Korean J. Soil Sci. Fert. Vol.52, No.4, pp.579-588, 2019 ...

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Korean J. Soil Sci. Fert. Vol.52, No.4, pp.579-588, 2019 Korean Journal of Soil Science and Fertilizer Article https://doi.org/10.7745/KJSSF.2019.52.4.579 pISSN : 0367-6315 eISSN : 2288-2162 Monitoring of Veterinary Antibiotics in the Agro-Environment Sung Chul Kim, Jin Wook Kim, Young Kyu Hong, Won il Kim 1 , and Oh Kyung Kwon 1 * Department of Bio-Environmental Chemistry, Chungnam National University, Daejeon 34134, Korea 1 Ojeong Eco-Resilience Institute, Korea University, Seoul 02841, Korea *Corresponding author: [email protected] A B S T R A C T Received: November 22, 2019 Revised: December 5, 2019 Accepted: December 6, 2019 Antibiotics has been recognized as an emerging contaminant in the agro-environment such as soil, irrigation water, and plant because of antibiotic resistance gene production. However, information about residual of antibiotics in the agro-environment is limited. Thus, antibiotic concentration in soil and cultivated plant was monitored in the two different region. Total of 7 different location was selected for soil and plant sampling and 6 antibiotics classified with tetracyclines (TCs) and sulfonamides (SAs) were analyzed. Result showed that all TCs and SAs were detected at least 2 locations while SMZ (sulfamethazine) and SMX (sulfamethoxazole) were not dected in the plant sample. Concentration range of TC and SA in the soil was 0.58 - 3.34, 0.12 - 3.02 ยตg kg -1 respectively. In case of plant, residual concentration was ranged 15.1 - 194.0, 24.9 - 36.3 ยตg kg -1 . Depending on antibiotic properties and physicochemical properties of soil, residual amount of antibiotics in soil and plant was varied. Overall, antibiotics could be detected in the agri-environment and best management practice should be conducted for minimizing adverse effect of antibiotics on ecosystem and human health. Keywords: Antibiotics, Soil, Plant, Agro-environement Antibiotics in soil and bioaccumulation through plant uptake. โ’ธ The Korean Society of Soil Science and Fertilizer. This is an Open Access article distributed under the terms of the Creative Commons Attribution Non- Commercial License (http://creativecommons.org/licenses/by-nc/4.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Transcript of Korean J. Soil Sci. Fert. Vol.52, No.4, pp.579-588, 2019 ...

Page 1: Korean J. Soil Sci. Fert. Vol.52, No.4, pp.579-588, 2019 ...

Korean J. Soil Sci. Fert. Vol.52, No.4, pp.579-588, 2019

Korean Journal of Soil Science and Fertilizer

Articlehttps://doi.org/10.7745/KJSSF.2019.52.4.579

pISSN : 0367-6315 eISSN : 2288-2162

Monitoring of Veterinary Antibiotics in the Agro-Environment

Sung Chul Kim, Jin Wook Kim, Young Kyu Hong, Won il Kim1, and Oh Kyung Kwon

1*

Department of Bio-Environmental Chemistry, Chungnam National University, Daejeon 34134, Korea1Ojeong Eco-Resilience Institute, Korea University, Seoul 02841, Korea

*Corresponding author: [email protected]

A B S T R A C T

Received: November 22, 2019

Revised: December 5, 2019

Accepted: December 6, 2019

Antibiotics has been recognized as an emerging contaminant in the agro-environment such as soil, irrigation

water, and plant because of antibiotic resistance gene production. However, information about residual of

antibiotics in the agro-environment is limited. Thus, antibiotic concentration in soil and cultivated plant was

monitored in the two different region. Total of 7 different location was selected for soil and plant sampling

and 6 antibiotics classified with tetracyclines (TCs) and sulfonamides (SAs) were analyzed. Result showed

that all TCs and SAs were detected at least 2 locations while SMZ (sulfamethazine) and SMX (sulfamethoxazole)

were not dected in the plant sample. Concentration range of TC and SA in the soil was 0.58 - 3.34, 0.12 - 3.02

ยตg kg-1

respectively. In case of plant, residual concentration was ranged 15.1 - 194.0, 24.9 - 36.3 ยตg kg-1

.

Depending on antibiotic properties and physicochemical properties of soil, residual amount of antibiotics in

soil and plant was varied. Overall, antibiotics could be detected in the agri-environment and best management

practice should be conducted for minimizing adverse effect of antibiotics on ecosystem and human health.

Keywords: Antibiotics, Soil, Plant, Agro-environement

Antibiotics in soil and bioaccumulation through plant uptake.

โ’ธ The Korean Society of Soil Science and Fertilizer. This is an Open Access article distributed under the terms of the Creative Commons Attribution Non- Commercial License (http://creativecommons.org/licenses/by-nc/4.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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580 โˆ™ Korean Journal of Soil Science and Fertilizer Vol. 52, No. 4, 2019

Introduction

ํ•ญ์ƒ์ œ (antibiotics)๋Š” ์ฃผ๋กœ ์ธ๊ฐ„๊ณผ ๊ฐ€์ถ•์˜ ์งˆ๋ณ‘ ์˜ˆ๋ฐฉ, ์น˜๋ฃŒ์˜ ๋ชฉ์ ์œผ๋กœ ์‚ฌ์šฉ๋˜๊ณ  ๊ทธ ์™ธ์—๋„ ๊ฐ€์ถ•์˜ ์„ฑ์žฅ ์ด‰์ง„์šฉ์œผ๋กœ

๋งŽ์ด ์‚ฌ์šฉ๋˜์–ด์ง„๋‹ค (Wang et al., 2015; Chen et al., 2016). ๊ทธ๋Ÿฌ๋‚˜ ํ™˜๊ฒฝ ์ค‘์— ํ•ญ์ƒ์ œ์˜ ์ž”๋ฅ˜๋กœ ์ธํ•œ ํ•ญ์ƒ์ œ ์ €ํ•ญ ๋ฐ•ํ…Œ๋ฆฌ

์•„ ์ƒ์„ฑ๊ณผ ๊ฐ™์€ ๋ฌธ์ œ๊ฐ€ ๋ฐœ์ƒํ•˜๋ฉด์„œ 1980๋…„ ๋ง๋ถ€ํ„ฐ ํ•ญ์ƒ์ œ๋ฅผ ์‹ ์ข… ์˜ค์—ผ๋ฌผ์งˆ (emerging contaminants)๋กœ ๊ฐ„์ฃผํ•˜์˜€๋‹ค.

ํ•ญ์ƒ์ œ๊ฐ€ ํ™˜๊ฒฝ ๋‚ด์— ์ž”๋ฅ˜ํ•˜๊ฒŒ ๋˜๋Š” ์ฃผ์š” ๊ฒฝ๋กœ๋Š” ์ธ๊ฐ„๊ณผ ๊ฐ€์ถ•์— ์‚ฌ์šฉ๋œ ํ›„ ํ™˜๊ฒฝ์— ๋ฐฐ์ถœ๋˜๋Š” ๊ฒฝ๋กœ, ์ˆ˜์‚ฐ์šฉ์œผ๋กœ ์‚ฌ์šฉ

๋˜๋Š” ํ•ญ์ƒ์ œ๊ฐ€ ์ˆ˜๊ณ„ ๋‚ด๋กœ ์œ ์ž…๋˜๋Š” ๊ฒฝ๋กœ, ๊ทธ๋ฆฌ๊ณ  ํ•ญ์ƒ์ œ๊ฐ€ ์ƒ์‚ฐ๋˜๋Š” ๊ณผ์ •์—์„œ ์ง์ ‘ ์œ ์ถœ๋˜๋Š” ๊ฒฝ๋กœ ๋“ฑ ํฌ๊ฒŒ 3๊ฐ€์ง€๋กœ ๋‚˜

๋‰  ์ˆ˜ ์žˆ๋‹ค. ํ™˜๊ฒฝ์— ์œ ์ž…๋œ ํ•ญ์ƒ์ œ๋Š” ์ฃผ๋กœ ํ† ์–‘์— ์œ ์ž…๋˜๋ฉฐ ๋†์—…์šฉ์ˆ˜ ๋˜๋Š” ๊ฐ•์šฐ์— ์˜ํ•ด ์ฃผ๋ณ€ ํ™˜๊ฒฝ์œผ๋กœ ์ด๋™ํ•œ๋‹ค (Pan

and Chu, 2016). ๋˜ํ•œ ์ธ๊ฐ„๊ณผ ๊ฐ€์ถ•์—๊ฒŒ ํˆฌ์—ฌ๋˜๋Š” ํ•ญ์ƒ์ œ๋Š” 10 - 20%๋งŒ์ด ์ƒ์ฒด ๋‚ด์—์„œ ํ™œ์šฉ๋˜๊ณ , 80 - 90%๊ฐ€ ์†Œ๋ณ€, ๋Œ€

๋ณ€ ๋“ฑ์˜ ๋ถ„๋‡จ์˜ ํ˜•ํƒœ๋กœ ๋ฐฐ์ถœ๋œ๋‹ค (Kim et al., 2017).

๋†์ดŒ ์ง€์—ญ ์ง€ํ•˜์ˆ˜์˜ ์ฃผ์š” ์˜ค์—ผ์›์€ ๋†๊ฒฝ์ง€์— ์‚ฌ์šฉ๋œ ๋น„๋ฃŒ ๋˜๋Š” ๋†์•ฝ, ๊ทธ๋ฆฌ๊ณ  ์ถ•์‚ฐํ์ˆ˜ ๋ฐ ๊ฐ€์ถ• ๋ถ„๋‡จ ๋“ฑ์ด์ง€๋งŒ ์ตœ๊ทผ

๊ฐ€์ถ• ๋งค๋ชฐ์ง€์˜ ์นจ์ถœ์ˆ˜์— ์˜ํ•œ ๋ณ‘์›์„ฑ ๋ฏธ์ƒ๋ฌผ, ํ•ญ์ƒ์ œ ๋˜๋Š” ํ•ญ์ƒ์ œ ์ €ํ•ญ ์œ ์ „์ž (ARG, Antibiotic Resistance Genes)

์™€ ๊ฐ™์€ ์‹ ์ข…์˜ค์—ผ๋ฌผ์งˆ์˜ ๋†์ดŒ ์ง€ํ•˜์ˆ˜ ์œ ์ž… ๊ฐ€๋Šฅ์„ฑ์ด ๋†’์•„์ง€๊ณ  ์žˆ๋‹ค (Michael et al., 2014).

ํ† ์–‘ ๋‚ด ์ž”๋ฅ˜ํ•˜๋Š” ํ•ญ์ƒ์ œ์˜ ์ž”๋ฅ˜ ๋†๋„๋Š” ํ•ญ์ƒ์ œ ์ž์ฒด์˜ ํŠน์„ฑ, ํ† ์–‘์˜ ๋ฌผ๋ฆฌ, ํ™”ํ•™์  ํŠน์„ฑ์— ๋”ฐ๋ผ ๋งค์šฐ ๋‹ค์–‘ํ•˜๋‹ค. ํŠนํžˆ

ํ•ญ์ƒ์ œ์˜ ๋ถ„์ž์  ๊ตฌ์กฐ, ๊ทน์„ฑ ๋˜๋Š” ๋น„๊ทน์„ฑ ํŠน์„ฑ, ๊ทธ๋ฆฌ๊ณ  ์นœ์ˆ˜์„ฑ ๋˜๋Š” ์†Œ์ˆ˜์„ฑ๊ณผ ๊ฐ™์€ ํŠน์„ฑ์— ๋”ฐ๋ผ ํ† ์–‘ ์ž…์ž์— ํก์ฐฉ์ด ์ž˜

์ผ์–ด๋‚˜๊ฑฐ๋‚˜ ํ† ์–‘๊ณผ ํก์ฐฉํ•˜์ง€ ์•Š๊ณ  ํ† ์–‘ ์ปฌ๋Ÿผ์„ ํ†ตํ•ด ์ง€ํ•˜์ˆ˜๋กœ ์œ ์ž…๋˜๊ธฐ๋„ ํ•œ๋‹ค. ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ๋Š”

์ˆ˜์‚ฐํ™” (-OH), ์•„๋ฏธ๋…ธ (-NH2), ๊ทธ๋ฆฌ๊ณ  ์ผ€ํ†ค (-CO)๊ณผ ๊ฐ™์€ ์ž‘์šฉ๊ธฐ๊ฐ€ 4๊ฐœ์˜ ๋ฒค์   ๊ณ ๋ฆฌ์™€ ๊ฒฐํ•ฉ๋œ ํ˜•ํƒœ์ด๋ฉฐ ํ† ์–‘ ์œ ๊ธฐ๋ฌผ

์„ ๊ฒฐํ•ฉ์ฒด๋กœ ํ•˜์—ฌ ์–‘์ด์˜จ ๊ตํ™˜๊ณผ ๊ฐ™์€ ๋ฉ”์ปค๋‹ˆ์ฆ˜์œผ๋กœ ํ† ์–‘ ์ž…์ž์— ํก์ฐฉ ํ•œ๋‹ค (Li et al., 2016; Ye et al., 2017). ์„คํฐ์•„๋งˆ

์ด๋“œ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ๋Š” 4-aminophenylsulfonylamide ํ˜•ํƒœ๋ฅผ ๊ฐ€์ง€๊ณ  ์žˆ์–ด ํ† ์–‘์— ํก์ฐฉ๋˜๊ธฐ ๋ณด๋‹ค๋Š” ์ด๋™์ด ์‰ฝ๋‹ค (Kim

and Kan, 2016; Riaz et al., 2018).

ํ† ์–‘์— ์œ ์ž…๋œ ํ•ญ์ƒ์ œ๋Š” ์ž‘๋ฌผ์— ์ „์ด๋˜๊ธฐ๋„ ํ•œ๋‹ค. ํ† ์–‘์—์„œ ์ž‘๋ฌผ์— ํก์ˆ˜๋œ ํ•ญ์ƒ์ œ๋Š” ์ž‘๋ฌผ์˜ ๋ฟŒ๋ฆฌ, ์ค„๊ธฐ, ์žŽ, ๊ณผ์‹ค ๋“ฑ

์— ์ถ•์ ๋˜๋ฉฐ ์ž‘๋ฌผ์ฒด์— ์ถ•์ ๋˜๋Š” ํ•ญ์ƒ์ œ๋Š” ํ•ญ์ƒ์ œ์˜ Kow๊ฐ’์— ๋”ฐ๋ผ ๋‹ฌ๋ผ์ง„๋‹ค. ์ผ๋ฐ˜์ ์œผ๋กœ Kow ๊ฐ’์ด ํฐ ์†Œ์ˆ˜์„ฑ ํ•ญ์ƒ

์ œ์˜ ๊ฒฝ์šฐ ์ฒด๊ด€ (phloem)์„ ํ†ตํ•ด ์ด๋™ํ•˜์—ฌ ๊ณผ์‹ค์— ์ถ•์ ๋˜๋Š” ๋ฐ˜๋ฉด Kow ๊ฐ’์ด ์ ์€ ์นœ์ˆ˜์„ฑ ํ•ญ์ƒ์ œ์˜ ๊ฒฝ์šฐ ๋ชฉ์งˆ๋ถ€

(xylem)๋ฅผ ํ†ตํ•ด ์ด๋™ํ•˜์—ฌ ์ฃผ๋กœ ์žŽ ๋˜๋Š” ๊ณผ์‹ค์— ์ถ•์  ๋œ๋‹ค (Miller et al., 2016).

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ๋†์ดŒ์ง€์—ญ์˜ ๋†์—…ํ™˜๊ฒฝ ์ค‘ ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด์— ์ž”๋ฅ˜ํ•˜๋Š” ํ•ญ์ƒ์ œ๋ฅผ ๋ชจ๋‹ˆํ„ฐ๋งํ•˜์˜€์œผ๋ฉฐ ์„ ํ–‰์—ฐ๊ตฌ์™€์˜ ๋น„๊ต

๋ฅผ ํ†ตํ•ด ๊ตญ๋‚ด ๋†์—…ํ™˜๊ฒฝ์—์„œ์˜ ํ•ญ์ƒ์ œ ์ž”๋ฅ˜ ํŠน์„ฑ์„ ํ‰๊ฐ€ํ•˜์˜€๋‹ค.

Materials and Methods

์‹œ์•ฝ ๋ฐ ์žฌ๋ฃŒ ํ•ญ์ƒ์ œ๋Š” ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด (Tetracyclines)๊ณผ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด (Sulfonamides)์˜ ํ•ญ์ƒ์ œ

์ค‘ 6์ข…์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๊ฐ ํ•ญ์ƒ์ œ ์ค‘ SMZ (sulfamethazine)(57-68-1 โ‰ฅ 99%), CTC (chlorotetracycline hydrochloride)

(64-72-2 โ‰ฅ 90%), TC (tetracycline hydrochloride)(67-75-5 โ‰ฅ 98%), OTC (oxytetracycline hydrochloride)(2058-

46-0 โ‰ฅ 95%)๋Š” Sigma-Aldrich (USA)์˜ ์ œํ’ˆ์„ ์‚ฌ์šฉํ•˜์˜€๊ณ , STZ (sulfathiazole)(72-14-0 โ‰ฅ 98%), SMX (sulfa-

methoxazole)(723-46-6 โ‰ฅ 97%)์€ FLUKA (USA)์˜ ์ œํ’ˆ์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ์‹œ๋ฃŒ ์ถ”์ถœ์šฉ๋งค๋กœ ์‚ฌ์šฉ๋œ ๋ฉ”ํƒ„์˜ฌ (DAEJUNG,

67-56-1, Korea)๊ณผ ์•„์„ธํ† ๋‚˜์ดํŠธ๋ฆด (DAEJUNG, 75-05-8, Korea)์€ HPLC ๋“ฑ๊ธ‰์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๊ณ ํ˜•์ƒ ์ถ”์ถœ๋ฒ• (SPE,

solid phase extraction)์— ์‚ฌ์šฉ๋œ ์นดํŠธ๋ฆฌ์ง€๋Š” Oasis HLB ์นดํŠธ๋ฆฌ์ง€ (Waters, 30 cc, 60 mg, USA)๋ฅผ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ, ๋‚ด

๋ถ€ ํ‘œ์ค€๋ฌผ์งˆ๋กœ๋Š” Accustandard์‚ฌ์˜ Simeton (673-04-1, 100 ยตg mL-1

, USA)์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค.

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Monitoring of Veterinary Antibiotics in the Agro-Environment โˆ™ 581

Fig. 1. Sampling location (a) Bong-Ha, (b) Pyeong-chang region.

์‹œ๋ฃŒ์ฑ„์ทจ ๋ฐ ์ „์ฒ˜๋ฆฌ ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ๋ฅผ ๋ชจ๋‹ˆํ„ฐ๋ง ํ•˜๊ธฐ ์œ„ํ•ด ๊ฒฝ๋ถ ๋ด‰ํ™” ์ง€์—ญ (3์ง€์ )๊ณผ ๊ฐ•์›๋„ ํ‰

์ฐฝ ์ง€์—ญ (5์ง€์ )์˜ ๊ฐ€์ถ• ๋†์žฅ ์ธ๊ทผ ๋†๊ฒฝ์ง€์—์„œ ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด๋ฅผ ์ฑ„์ทจํ•˜์˜€๋‹ค (Fig. 1). ํ† ์–‘ ์‹œ๋ฃŒ๋Š” ํ‘œ์ธต์˜ ์œ ๊ธฐ๋ฌผ์„ ์ œ

๊ฑฐํ•œ ํ›„ ํœด๋Œ€์šฉ ํ† ์–‘์ฑ„์ทจ๊ธฐ๋ฅผ ์ด์šฉํ•˜์—ฌ 0 - 15 cm์˜ ํ† ์–‘์„ ์ฑ„์ทจํ•˜์˜€๋‹ค. ๊ฐ ์ง€์ ๋ณ„ ๋Œ€ํ‘œ ์‹œ๋ฃŒ๋Š” ์‹œ๋ฃŒ ์ฑ„์ทจ ์ง€์  100

m2๋‚ด์—์„œ 5๊ตฐ๋ฐ์˜ ํ† ์–‘์„ ์ฑ„์ทจํ•œ ํ›„ ํ•˜๋‚˜์˜ ์‹œ๋ฃŒ ์ฑ„์ทจ ์šฉ๊ธฐ์— ํ•ฉํ•˜์—ฌ ๋งŒ๋“ค์—ˆ๋‹ค.

์ž‘๋ฌผ์ฒด ์‹œ๋ฃŒ๋Š” ํ† ์–‘ ์ฑ„์ทจ ์ง€์ ๊ณผ ๊ฐ™์€ ์ง€์ ์—์„œ ์žฌ๋ฐฐ๋˜๋Š” ์ž‘๋ฌผ์ฒด๋ฅผ ์ฑ„์ทจํ•˜์˜€์œผ๋ฉฐ ์ฑ„์ทจ ์ž‘๋ฌผ์€ ๊ณ ๊ตฌ๋งˆ, ๋ฌด, ์ˆ˜์ˆ˜, ๊ฐ

์ž, ํŒŒ, ๊ณ ์ถ”, ๋‹น๊ท€ ๋“ฑ ๋‹ค์–‘ํ•œ ์ž‘๋ฌผ์ฒด๋ฅผ ์ฑ„์ทจํ•˜์˜€๋‹ค. ๊ฐ ์ž‘๋ฌผ์ฒด๋Š” ๊ฐ€์‹๋ถ€๋ถ„๋งŒ์„ ์ฑ„์ทจํ•˜์˜€์œผ๋ฉฐ ์ž‘๋ฌผ์ฒด๋ณ„ 2 - 3๊ฐœ์˜ ์‹œ๋ฃŒ

๋ฅผ ์ฑ„์ทจํ•˜์˜€๋‹ค.

์ฑ„์ทจ๋œ ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด๋Š” ์•„์ด์ŠคํŒฉ์ด ๋‹ด๊ธด ์•„์ด์Šค๋ฐ•์Šค์— ๋‹ด์€ ํ›„ ์‹คํ—˜์‹ค๋กœ ์šด๋ฐ˜๋˜์—ˆ๋‹ค. ํ† ์–‘ ์‹œ๋ฃŒ๋Š” ์‹ค์˜จ (18 - 20ยฐC)

์˜ ์•”์กฐ๊ฑด์—์„œ ์ˆ˜๋ถ„ํ•จ๋Ÿ‰์ด 5% ๋ฏธ๋งŒ์ด ๋  ๋•Œ๊นŒ์ง€ ์•ฝ 3 - 5์ผ ํ’๊ฑดํ•œ ํ›„ 2 mm๋กœ ์ฒด๊ฑฐ๋ฆ„ํ•˜์—ฌ 4ยฐC์—์„œ ๋ƒ‰์žฅ ๋ณด๊ด€ํ•˜์˜€๋‹ค.

์ž‘๋ฌผ์ฒด ์‹œ๋ฃŒ๋Š” ๊ฐ€์‹ ๋ถ€๋ถ„์„ ์ฆ๋ฅ˜์ˆ˜๋กœ 3๋ฒˆ ์„ธ์ฒ™ํ•œ ํ›„ ์ข…์ด ํƒ€์›”์„ ์ด์šฉํ•˜์—ฌ ๋ฌผ๊ธฐ๋ฅผ ์ œ๊ฑฐํ•˜์˜€๋‹ค. ๊ฐ ์ž‘๋ฌผ์ฒด๋Š” ์กฐ๊ฐ์œผ

๋กœ ์„ธ๋ถ„ํ™”ํ•œ ํ›„ -80ยฐC์—์„œ 3์ผ๊ฐ„ ๋ƒ‰๋™ ํ›„ ๋™๊ฒฐ๊ฑด์กฐ ๊ณผ์ •์„ ๊ฑฐ์ณ ๋ง‰์ž์‚ฌ๋ฐœ์„ ์ด์šฉํ•˜์—ฌ ํŒŒ์‡„ํ•˜์˜€๋‹ค. ํŒŒ์‡„ํ•œ ์ž‘๋ฌผ์ฒด ์‹œ

๋ฃŒ๋Š” ๋ฏน์„œ๊ธฐ๋ฅผ ์ด์šฉํ•˜์—ฌ ๊ณฑ๊ฒŒ ํŒŒ์‡„ํ•œ ํ›„ 4ยฐC์—์„œ ๋ƒ‰์žฅ ๋ณด๊ด€ํ•˜์˜€๋‹ค.

ํ† ์–‘์˜ ํ™”ํ•™์  ํŠน์„ฑ ๋ถ„์„ ํ† ์–‘์˜ pH์™€ ์ „๊ธฐ์ „๋„๋„ (EC)๋Š” ํ’๊ฑดํ† ์–‘ 10 g์— ์ฆ๋ฅ˜์ˆ˜ 50 mL์„ ๊ฐ€ํ•˜์—ฌ 1์‹œ๊ฐ„ ์ง„

ํƒ•ํ•˜๊ณ  Whatman No.2๋กœ ์—ฌ๊ณผํ•œ ํ›„ pH meter (MP220, METTLER TOLEDO)์™€ EC meter (Conductivity Meter

S230, METTLER TOLEDO)๋ฅผ ์ด์šฉํ•˜์—ฌ ์ธก์ •ํ•˜์˜€๋‹ค. ์œ ๊ธฐ๋ฌผ ํ•จ๋Ÿ‰์€ Walkley & Black๋ฒ•์— ์ค€ํ•˜์—ฌ 1N K2Cr2O7์„

๊ฐ€ํ•˜์—ฌ ๋ฐ˜์‘์‹œํ‚จ ํ›„ UV/Vis Spectrophotometer (UV 240 Schimadzu, Japan)๋กœ ํŒŒ์žฅ 610 nm์—์„œ ๋น„์ƒ‰ ์ •๋Ÿ‰ํ•˜์˜€๋‹ค.

์ถ”์ถœ, ๋†์ถ•, ๋ฐ ๊ธฐ๊ธฐ๋ถ„์„ ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ ์ถ”์ถœ ๋ฐ ๋†์ถ• ๋ฐฉ๋ฒ•์€ ์„ ํ–‰ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋ฅผ ์ด์šฉํ•˜์˜€๋‹ค (Kim

et al., 2018). ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด ๋‚ด ํ•ญ์ƒ์ œ๋ฅผ ์ถ”์ถœํ•˜๊ธฐ ์œ„ํ•ด ๊ฐ๊ฐ 1, 0.1g์„ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ ์ถ”์ถœ์ œ๋Š” Mcllvaine ์™„์ถฉ์šฉ์•ก์„

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582 โˆ™ Korean Journal of Soil Science and Fertilizer Vol. 52, No. 4, 2019

Table 1. parameters of high performance liquid chromatography MS/MS for quantification of veterinary antibiotics in

groundwater near at rural area.

Equipment Agilent 1200 High performance liquid chromatograph-

API 4000 liquid chromatograph Tandem Mass spectrometry

HPLC Column Zorbax Eclipse Plus-C18 3.5 ยตm (4.6 ร— 150 mm)

Guard Column Security Guard catridge Kit

Column temperature 25ยฐC

Mobile Phase A : 99.9% HPLC grade water + 0.1% formic acid (v/v)

B : 99.9% acetonitrile + 0.1% formic acid (v/v)

Flow rate 0.7 mL/min

Inject volume 5 ยตL

Gradient condition 0 min : A 90% + B 10%

2 min : A 90% + B 10%

8 min : A 50% + B 50%

10 min : A 100% + B 0%

11 min : A 0% + B 100%

11.1 min : A 90% + B 10%

15 min : A 90% + B 10%

MS/MS Mode Electronic Spray Ionisation (ESI)

Drying and Nebulizer gas Nitrogen gas

Drying gas flow 10.0 L/min

Drying gas temperature 350ยฐC

Capillary Voltage 5,500 V

์‚ฌ์šฉํ•˜์˜€๋‹ค. ์ถ”์ถœ๋œ ์™„์ถฉ์šฉ์•ก์„ ์ •์ œํ•˜๊ธฐ ์œ„ํ•ด ๊ณ ํ˜•์ƒ ์ถ”์ถœ๋ฒ• (SPE)์„ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ ์ •์ œ๋œ ์‹œ๋ฃŒ๋Š” ์งˆ์†Œ ๋†์ถ•๊ธฐ

(N-Evap-11, USA)๋ฅผ ์ด์šฉํ•˜์—ฌ 50 ยตL๋กœ ๋†์ถ•ํ•œ ํ›„ ์ด๋™์ƒ ์šฉ์•ก (์ฆ๋ฅ˜์ˆ˜ 99.9% + formic acid 0.1%) 70 ยตL๋ฅผ ํ˜ผํ•ฉํ•˜

์—ฌ ์ตœ์ข… ๋ถ„์„ ์‹œ๋ฃŒ๋Š” 120 ยตL๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค.

ํ•ญ์ƒ์ œ ๋ถ„์„์— ์‚ฌ์šฉ๋œ ๊ธฐ๊ธฐ๋Š” ์ถฉ๋‚จ๋Œ€ํ•™๊ต ๊ณต๋™์‹คํ—˜์‹ค์Šต๊ด€์˜ High Performance Liquid Chromatography Tandem

Mass Spectrometer (HPLC/MS/MS, 4000 Q trap, ABSCIEX, USA)๋ฅผ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ, ์ด๋™์ƒ์˜ ์กฐ์„ฑ์€ A, 99.9%

HPLC grade water + 0.1% formic acid (v/v); B, 99.9% acetonitrile + 0.1% formic acid (v/v)๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ์‚ฌ์šฉ๋œ

์ปฌ๋Ÿผ์€ ์ž…๊ฒฝ ํฌ๊ธฐ (pore size)๊ฐ€ 3.5 ยตm์ด๋ฉฐ, ๋‚ด๊ฒฝ์ด 4.6 mm์ธ Zorbax Eclipse Plus-C18 (Agilent Technologies, USA)

์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ํ•ญ์ƒ์ œ ๋ถ„์„์„ ์œ„ํ•œ HPLC/MS/MS ์กฐ๊ฑด์€ Tables 1, 2์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

์ž”๋ฅ˜ ํ•ญ์ƒ์ œ ๋ถ„์„์˜ ํšจ์œจ์„ ๊ทน๋Œ€ํ™”ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ compound optimization์„ ์‹ค์‹œํ•˜์˜€๋‹ค. ํ•ญ์ƒ์ œ ์ข…๋ฅ˜๋ณ„๋กœ 1 mg L-1

์˜ ํ‘œ์ค€์šฉ์•ก์„ ์กฐ์ œํ•˜์—ฌ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ, ํ•ญ์ƒ์ œ์˜ ๋ถ„์ž์‹์„ ์ž…๋ ฅํ•˜์—ฌ ์‚ฐ์ถœ๋œ exact mass๊ฐ’์„ ๋Œ€์ž…ํ•˜์˜€๋‹ค. ๊ทธ ํ›„ ์„ ๊ตฌ

์ด์˜จ (precursor ion)์— ๋”ฐ๋ฅธ ์ƒ์„ฑ์ด์˜จ (product ion)์„ ํ™•์ธํ•˜์˜€๊ณ , Colloision energy (CE)์™€ Deculstering Potential

(DP)์— ๋ณ€ํ™”๋ฅผ ์ฃผ์–ด ๊ฐ ํ•ญ์ƒ์ œ์˜ ์ƒ์„ฑ์ด์˜จ์˜ ๊ฐ๋„๋ฅผ ์ฆ๊ฐ€์‹œ์ผฐ์œผ๋ฉฐ ๋ถ„์„ํšจ์œจ์ด ์ฆ๋Œ€๋œ ์ตœ์  ์กฐ๊ฑด์„ ํ™•๋ฆฝํ•˜์˜€๋‹ค

(Table 3).

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Monitoring of Veterinary Antibiotics in the Agro-Environment โˆ™ 583

Table 2. parameters of high performance liquid chromatography MS/MS for quantification of veterinary antibiotics in

groundwater near at rural area.

Equipment Agilent 1200 High performance liquid chromatograph-

API 4000 liquid chromatograph Tandem Mass spectrometry

HPLC Column Zorbax Eclipse XDB-C18 5 ยตm (2.1 ร— 150 mm)

Guard Column Security Guard catridge Kit

Column temperature 30ยฐC

Mobile Phase A : 99.9% HPLC grade water + 0.1% formic acid (v/v)

B : 99.9% acetonitrile + 0.1% formic acid (v/v)

Flow rate 0.5 mL/min

Inject volume 10 ยตL

Gradient condition 10 min : A 6% + B 94%

MS/MS Mode Electronic Spray Ionisation (ESI)

Drying and Nebulizer gas Nitrogen gas

Drying gas flow 10.0 L/min

Drying gas temperature 300ยฐC

Capillary Voltage 5,500 V

Table 3. Fragmented ions of nine veterinary antibiotics and internal standard depending on colloision energy and

deculstering energy.

Antibioticsprecursor ion

[M+H]+

(m/z)

product ion

(m/z)CE DP

SIMETON 198.125 100.1 39 66

124.1 27

128.1 27

SMZ 279.068 124.2 33 31

156.2 31

186.1 25

CTC 479.133 302.8 55 46

443.8 31

462.0 29

TC 445.228 410.0 25 76

427.1 19

428.1 21

SMX 254.083 108.1 37 46

147.1 21

156.2 21

STZ 256.019 101.1 39 1

108.1 37

156.0 27

OTC 461.176 201.1 47 41

282.9 49

426.2 29

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584 โˆ™ Korean Journal of Soil Science and Fertilizer Vol. 52, No. 4, 2019

Table 4. Chemical properties of examined soil.

NamepH EC SOM

(1:5) mS cm-1

%

B_S1 6.12 ยฑ 0.57 0.25 ยฑ 0.03 1.29 ยฑ 0.17

B_S2 6.39 ยฑ 0.08 0.26 ยฑ 0.00 3.99 ยฑ 0.18

B_S3 5.35 ยฑ 0.10 0.37 ยฑ 0.02 2.18 ยฑ 0.09

P_S1 5.76 ยฑ 0.06 1.98 ยฑ 0.04 2.06 ยฑ 0.05

P_S2 6.64 ยฑ 0.03 0.13 ยฑ 0.00 1.88 ยฑ 0.07

P_S3 5.32 ยฑ 0.02 2.52 ยฑ 0.10 2.16 ยฑ 0.05

P_S4 6.45 ยฑ 0.19 0.65 ยฑ 0.01 1.90 ยฑ 0.39

P_S5 5.16 ยฑ 0.12 0.70 ยฑ 0.04 2.53 ยฑ 0.26

QA/QC ๋ฐ ํ†ต๊ณ„์ฒ˜๋ฆฌ ํ•ญ์ƒ์ œ ๋ถ„์„ ๋ฐฉ๋ฒ•์˜ QA/QC๋ฅผ ์œ„ํ•ด ํšŒ์ˆ˜์œจ ๊ฒ€์ •์„ ์‹ค์‹œํ•˜์˜€๋‹ค. ํšŒ์ˆ˜์œจ ๊ฒ€์ •์„ ์œ„ํ•ด ๋Œ€์กฐ

๊ตฌ (ํ•ญ์ƒ์ œ๊ฐ€ ๋“ค์–ด์žˆ์ง€ ์•Š์€ ์ˆœ์ˆ˜ํ•œ ์ฆ๋ฅ˜์ˆ˜)๋ฅผ ์ „์ฒ˜๋ฆฌ ํ•œ ํ›„ ํ•ญ์ƒ์ œ๋ฅผ ์ธ์œ„์ ์œผ๋กœ spikingํ•˜๋Š” ์‹œ์ ์„ ๊ฐ๊ฐ SPE ์ „๊ณผ

SPE ํ›„๋กœ ๋‹ฌ๋ฆฌํ•˜์˜€๋‹ค. ํšŒ์ˆ˜์œจ ์šฉ ์‹œ๋ฃŒ๋Š” ๊ฐ๊ฐ์˜ ๋†๋„์— SPE ์ „, ํ›„ spikingํ•˜๋Š” ์‹œ๋ฃŒ 2๊ฐœ์”ฉ 4๊ฐœ, ๋ฐ”ํƒ•์‹œ๋ฃŒ 1๊ฐœ๋ฅผ ํฌํ•จ

ํ•œ 5๊ฐœ๋ฅผ ์ค€๋น„ํ•˜์˜€๋‹ค. ํšŒ์ˆ˜์œจ์—๋Š” ํ•ญ์ƒ์ œ ๊ณ„์—ด ๋ณ„๋กœ ํ‘œ์ค€์šฉ์•ก์„ 0.1 mg L-1

๊ณผ 1 mg L-1๋กœ ์กฐ์ œํ•˜์—ฌ ์‹ค์‹œํ•˜์˜€๋‹ค. ํšŒ์ˆ˜

์œจ ๊ฒ€์ฆ์€ ๊ณต์‹ 1๊ณผ ๊ฐ™์ด ๊ตฌํ•˜์˜€๋‹ค.

ํšŒ์ˆ˜์œจ ํ›„์‹œ๋ฃŒ์— ํ•˜์—ฌ๊ฒ€์ถœ๋œ๋†๋„

์ „์‹œ๋ฃŒ์— ํ•˜์—ฌ๊ฒ€์ถœ๋œ๋†๋„ร— (Eq. 1)

๊ฒ€๋Ÿ‰์„ ์„ ์œ„ํ•œ ํ•ญ์ƒ์ œ standard ์šฉ์•ก์€ 0.01, 0.025, 0.05, 0.1, 0.25, 0.5, 1 mg L-1์˜ ๋†๋„๋กœ ์ œ์กฐํ•˜์˜€๋‹ค. ๋ชจ๋“  ๋ถ„์„

์€ 3๋ฐ˜๋ณต์„ ์‹ค์‹œํ•˜์˜€๋‹ค.

Results and Discussion

ํ† ์–‘์˜ ํ™”ํ•™์  ํŠน์„ฑ ํ† ์–‘ ์‹œ๋ฃŒ์˜ ํ™”ํ•™์  ํŠน์„ฑ์€ Table 4์— ์ •๋ฆฌํ•˜์˜€๋‹ค. ํ† ์–‘์˜ pH๋Š” 5.16 - 6.64์˜ ์•ฝ์‚ฐ์„ฑ ํŠน์„ฑ

์„ ๋‚˜ํƒ€๋ƒˆ์œผ๋ฉฐ ํ† ์–‘์˜ ์ „๊ธฐ์ „๋„๋„ (EC)๋Š” 0.25 - 2.52 mS cm-1์˜ ๋ฒ”์œ„๋ฅผ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ํ† ์–‘ ์œ ๊ธฐ๋ฌผ์˜ ํ•จ๋Ÿ‰์€ 1.29 -

3.99%์˜ ๋ฒ”์œ„๋ฅผ ๋‚˜ํƒ€๋‚ด ์ฑ„์ทจํ•œ ํ† ์–‘ ์‹œ๋ฃŒ์˜ ํ™”ํ•™์  ํŠน์„ฑ์€ ๋ฐญํ† ์–‘์˜ ์ ์ •๋ฒ”์œ„์— ํฌํ•จ๋˜์—ˆ๋‹ค.

ํ•ญ์ƒ์ œ ๋ถ„์„ QA/QC ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด ์‹œ๋ฃŒ์— ๋Œ€ํ•œ ํ•ญ์ƒ์ œ ๋ถ„์„์˜ ํšŒ์ˆ˜์œจ ๋ฐ ๊ฒ€์ถœํ•œ๊ณ„ (LOD)์— ๋Œ€ํ•œ ์ •๋ณด๋Š”

Table 5์— ์ •๋ฆฌํ•˜์˜€๋‹ค. ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด์˜ ํšŒ์ˆ˜์œจ ๋ฒ”์œ„๋Š” ๊ฐ๊ฐ 72 - 90%, 74 - 90%์˜€์œผ๋ฉฐ ๊ฒ€์ถœํ•œ๊ณ„๋Š” 0.05 - 0.24, 0.04 -

0.41 ยตg kg-1

์ด์—ˆ๋‹ค. ํ† ์–‘ ๋ฐ ์ž‘๋ฌผ์ฒด์˜ ํšŒ์ˆ˜์œจ์€ ๋ชจ๋‘ ์ ์ •๋ฒ”์œ„ (70 - 130%) ๋ฒ”์œ„๋ฅผ ๋งŒ์กฑํ•˜์˜€์œผ๋ฉฐ ๊ฒ€์ถœํ•œ๊ณ„ ์—ญ์‹œ ํ™˜

๊ฒฝ ๋‚ด ์ž”๋ฅ˜ํ•˜๋Š” ํ•ญ์ƒ์ œ์˜ ๊ฒ€์ถœ์— ์ถฉ๋ถ„ํ•œ ๊ฒ€์ถœ ํ•œ๊ณ„๋กœ ์กฐ์‚ฌ๋˜์—ˆ๋‹ค.

ํ† ์–‘ ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ ๋†๋„ ํ† ์–‘ ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ ๋†๋„๋Š” Table 6์— ์ •๋ฆฌํ•˜์˜€๋‹ค. ์ด 6์ข…๋ฅ˜์˜ ํ•ญ์ƒ์ œ ์ค‘ ๊ฒ€์ถœ ๋นˆ๋„

๊ฐ€ ๊ฐ€์žฅ ๋†’์€ ํ•ญ์ƒ์ œ๋Š” SMX, STZ, TC, OTC๋กœ ๋ถ„์„ํ•œ ํ† ์–‘ ์‹œ๋ฃŒ 8์ง€์ ์—์„œ ๋ชจ๋‘ ๊ฒ€์ถœ๋˜์—ˆ์œผ๋ฉฐ ๊ฒ€์ถœ ๋†๋„๋Š” ๊ฐ๊ฐ

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Monitoring of Veterinary Antibiotics in the Agro-Environment โˆ™ 585

Table 5. Recovery ratio and limit of quantification of each antibiotics.

AntibioticsSoil Plant

Recovery ratio (%) LOD (ยตg kg-1

) Recovery ratio (%) LOD (ยตg kg-1

)

SMZ 75 0.05 90 0.04

SMX 90 0.16 87 0.24

STZ 72 0.09 84 0.16

CTC 74 0.25 74 0.35

TC 83 0.19 83 0.41

OTC 83 0.24 84 0.23

Table 6. Antibiotic concentration in soil.

NameSMZ SMX STZ CTC TC OTC

ยตg kg-1

B_S1 1.39 ยฑ 1.11 2.42 ยฑ 0.09 2.96 ยฑ 0.34 ใ€€ 2.80 ยฑ 0.13 1.05 ยฑ 0.02

B_S2 0.58 ยฑ 0.81 3.02 ยฑ 0.81 2.76 ยฑ 0.09 2.09 ยฑ 0.14 2.89 ยฑ 0.41 1.40 ยฑ 0.26

B_S3 0.92 ยฑ 0.53 2.39 ยฑ 0.18 2.43 ยฑ 0.17 ใ€€ 2.54 ยฑ 1.04 1.09 ยฑ 0.08

P_S1 ใ€€ 2.60 ยฑ 0.17 3.22 ยฑ 0.19 ใ€€ 2.35 ยฑ 0.53 1.29 ยฑ 0.20

P_S2 ใ€€ 2.52 ยฑ 0.14 2.60 ยฑ 0.19 ใ€€ 3.13 ยฑ 0.26 1.09 ยฑ 0.10

P_S3 ใ€€ 2.80 ยฑ 0.51 2.86 ยฑ 0.11 0.58 ยฑ 0.15 2.32 ยฑ 0.15 2.30 ยฑ 0.26

P_S4 0.12 ยฑ 0.14 2.36 ยฑ 0.10 2.61 ยฑ 0.17 ใ€€ 3.05 ยฑ 0.01 3.34 ยฑ 0.30

P_S5 ใ€€ 2.39 ยฑ 0.03 2.76 ยฑ 0.19 ใ€€ 2.98 ยฑ 0.08 1.29 ยฑ 0.08

2.36 - 3.02, 2.43 - 3.22, 2.32 - 3.13, 1.05 - 3.34 ยตg kg-1์˜ ๋ฒ”์œ„๋กœ ๊ฒ€์ถœ๋˜์—ˆ๋‹ค. SMZ์˜ ๊ฒฝ์šฐ ๋ด‰ํ™”์ง€์—ญ์—์„œ๋Š” 0.58 - 1.39

ยตg kg-1์˜ ๋ฒ”์œ„๋กœ ๋ชจ๋“  ์ง€์ ์—์„œ ๊ฒ€์ถœ๋œ ๋ฐ˜๋ฉด ํ‰์ฐฝ ์ง€์—ญ์—์„œ๋Š” ์˜ค์ง P4์ง€์ ์—์„œ 0.12 ยตg kg

-1์œผ๋กœ ๊ฒ€์ถœ๋˜์—ˆ๋‹ค. CTC

์˜ ๊ฒฝ์šฐ ๋ด‰ํ™”์ง€์—ญ๊ณผ ํ‰์ฐฝ์ง€์—ญ ์ค‘ ๊ฐ๊ฐ 1์ง€์ ์—์„œ ๊ฒ€์ถœ๋˜์—ˆ์œผ๋ฉฐ ๊ฒ€์ถœ ๋†๋„๋Š” 2.09, 0.58 ยตg kg-1๋กœ ์กฐ์‚ฌ๋˜์–ด ๊ฒ€์ถœ ๋นˆ๋„

๊ฐ€ ๊ฐ€์žฅ ๋‚ฎ์•˜๋‹ค.

ํ† ์–‘ ๋‚ด ํ•ญ์ƒ์ œ์˜ ๋†๋„๋Š” ํ•ญ์ƒ์ œ์˜ ํก์ฐฉ ์ •๋„, ํ† ์„ฑ, ์œ ๊ธฐ๋ฌผ์˜ ํ•จ๋Ÿ‰ ๋“ฑ์— ๋”ฐ๋ผ ๋‹ค์–‘ํ•˜๊ฒŒ ๋ณด๊ณ ๋˜์—ˆ๋‹ค. ์ค‘๊ตญ ์–‘์ฏ”๊ฐ• ์œ 

์—ญ์˜ ๋†๊ฒฝ์ง€์—์„œ ์ด 25๊ฐœ์˜ ํ•ญ์ƒ์ œ ํ‰๊ท  ๋†๋„๋Š” 41.43 - 105.72 ยตg kg-1

์ˆ˜์ค€์œผ๋กœ ๊ฒ€์ถœ๋˜์—ˆ๊ณ  (Zhao et al., 2018a, 2018b),

์บ๋‚˜๋‹ค ์ง€์—ญ์—์„œ ๋ถ„๋‡จ๋ฅผ ๋†๊ฒฝ์ง€์— ํˆฌ์ž…ํ•˜์˜€์„ ๊ฒฝ์šฐ ํด๋กœ๋ฅดํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ์˜ ๋†๋„๊ฐ€ 754 ยตg kg-1

์ˆ˜์ค€์œผ๋กœ ๊ฒ€์ถœ๋˜

์—ˆ๋‹ค (Carlson and Mabury, 2006).

ํ† ์–‘์— ์ž”๋ฅ˜ํ•˜๋Š” ํ•ญ์ƒ์ œ๋Š” ์–‘์ด์˜จ ๊ตํ™˜ (cation exchange), ํ‘œ๋ฉด ๊ฒฐํ•ฉ (surface complexation), ๊ทธ๋ฆฌ๊ณ  ์ˆ˜์†Œ๊ฒฐํ•ฉ

(hydrogen bonding)๊ณผ ๊ฐ™์€ ๋ฉ”์ปค๋‹ˆ์ฆ˜์— ์˜ํ•ด ํ† ์–‘ ํ‘œ๋ฉด์— ํก์ฐฉ๋˜๋ฉฐ ํ•ญ์ƒ์ œ์˜ ํŠน์„ฑ (์นœ์ˆ˜์„ฑ, ์†Œ์ˆ˜์„ฑ, ์ด์˜จํ™”, ์ž‘์šฉ๊ธฐ)

์— ๋”ฐ๋ผ ํ† ์–‘ ์ž…์ž์™€์˜ ํก์ฐฉ๋ ฅ์ด ๊ฒฐ์ • ๋œ๋‹ค (Zhou et al., 2014). ํŠนํžˆ ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ๋Š” ๊ทน์„ฑ์„ ๋ ๋Š”

์ž‘์šฉ๊ธฐ (-COOH, -C=O, -CONH, -N(CH3)2, -OH)๋ฅผ ํฌํ•จํ•˜๊ณ  ์žˆ์–ด ํ† ์–‘ ๋‚ด 2๊ฐ€ ์–‘์ด์˜จ๊ณผ ๊ฐ•ํ•˜๊ฒŒ ๊ฒฐํ•ฉํ•˜๋Š” ํŠน์„ฑ์œผ๋กœ

์ธํ•ด ๋‹ค๋ฅธ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ์— ๋น„ํ•ด ํก์ฐฉ๋Šฅ์ด ๋†’์•„ ํ† ์–‘ ๋‚ด ์ž”๋ฅ˜ ํŠน์„ฑ์ด ๋†’์•˜๋‹ค (Gu et al., 2007; Wang and Wang, 2015).

์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ๋Š” ๋ถ„์ž ๊ตฌ์กฐ์ƒ ์ด์˜จํ™” ๋˜๊ธฐ ์‰ฌ์šด 2๊ฐœ์˜ ๊ตฌ์กฐ (์—ผ๊ธฐ์„ฑ์˜ 4-์•„๋ฏธ๋…ธ ๋ฐฉํ–ฅ์กฑ๊ณผ ์‚ฐ์„ฑ ์„คํฐ์•„

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586 โˆ™ Korean Journal of Soil Science and Fertilizer Vol. 52, No. 4, 2019

Table 7. Antibiotic concentration in crops.

Name Crops SMZ SMX STZ CTC TC OTC

ยตg kg-1

B_S1 Sweet potato ใ€€ ใ€€ 28.9 ยฑ 2.05 ใ€€ 37.4 ยฑ 6.23 15.1 ยฑ 0.56

B_S2 Sorghum ใ€€ ใ€€ 36.3 ยฑ 4.17 ใ€€ 48.7 ยฑ 13.2 ใ€€

B_S3 Radish ใ€€ ใ€€ 29.5 ยฑ 2.84 5.10 ยฑ 1.75 95.9 ยฑ 27.5 12.0 ยฑ 0.74

P_S1 Potato ใ€€ ใ€€ 25.7 ยฑ 1.57 ใ€€ 64.8 ยฑ 17.0 37.2 ยฑ 1.27

P_S2 Green onion ใ€€ ใ€€ 30.2 ยฑ 2.38 ใ€€ 112.0 ยฑ 30.3 23.0 ยฑ 4.17

P_S3 Pepper ใ€€ ใ€€ 24.9 ยฑ 1.02 ใ€€ 194.0 ยฑ 9.41 20.4 ยฑ 0.34

P_S4 Radish ใ€€ ใ€€ 28.8 ยฑ 3.40 ใ€€ 104.2 ยฑ 8.75 26.1 ยฑ 2.50

P_S5 Medicinal herbs ใ€€ ใ€€ 34.4 ยฑ 5.18 ใ€€ 28.6 ยฑ 7.65 ใ€€

์ž‘์šฉ๊ธฐ)๋กœ ๋˜์–ด ์žˆ์–ด ์ผ๋ฐ˜์ ์œผ๋กœ ํ† ์–‘ ํก์ฐฉ๋ ฅ์ด ๋‚ฎ๋‹ค (Pikkemaat et al., 2016).

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ํ† ์–‘ ๋‚ด ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด๊ณผ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ๊ฐ€ ๊ณ ๋ฃจ ๊ฒ€์ถœ๋˜์—ˆ๋‹ค. ํ† ์–‘ ๋‚ด ์ž”๋ฅ˜ ํ•ญ

์ƒ์ œ์˜ ๋†๋„๋Š” ํ† ์–‘ pH์™€๋„ ์ƒ๊ด€์„ฑ์ด ์žˆ๋‹ค. ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ๊ณผ ์„คํฐ์•„๋งˆ์ด๋“œ ํ•ญ์ƒ์ œ์˜ ๊ฒฝ์šฐ ํ† ์–‘์˜ pH๊ฐ€ ์‚ฐ์„ฑ ์กฐ

๊ฑด (pH < 7)์ผ ๊ฒฝ์šฐ ์ค‘์„ฑ ๋˜๋Š” ์–‘์ด์˜จ์˜ ํŠน์„ฑ์„ ๊ฐ€์ง„ ํ•ญ์ƒ์ œ๊ฐ€ ํ† ์–‘ ํ‘œ๋ฉด์— ํก์ฐฉํ•˜์—ฌ ๋ณด๋‹ค ์•ˆ์ •์ ์ธ ์ž”๋ฅ˜ ํŠน์„ฑ์„ ๊ฐ€์ง„

๋‹ค๊ณ  ๋ณด๊ณ ํ•˜์˜€๋‹ค (Schauss et al., 2009). ํ† ์–‘ ์‹œ๋ฃŒ ์ฑ„์ทจ ์ง€์  ์ด 8๊ณณ ๋ชจ๋‘ ํ† ์–‘ pH๊ฐ€ 7๋ณด๋‹ค ๋‚ฎ์€ ์‚ฐ์„ฑ ์กฐ๊ฑด์„ ๊ฐ€์ง€๊ณ 

์žˆ์–ด ๋‘ ์ข…๋ฅ˜์˜ ํ•ญ์ƒ์ œ๊ฐ€ ์•ˆ์ •์ ์œผ๋กœ ํก์ฐฉ๋˜์—ˆ์„ ๊ฒƒ์œผ๋กœ ์‚ฌ๋ฃŒ๋œ๋‹ค.

์ž‘๋ฌผ์ฒด ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ ๋†๋„ ์ด 6์ข…๋ฅ˜์˜ ํ•ญ์ƒ์ œ ์ค‘ ์ž‘๋ฌผ์ฒด ๋‚ด์—์„œ ๊ฒ€์ถœ ๋นˆ๋„๊ฐ€ ๊ฐ€์žฅ ๋†’์€ ํ•ญ์ƒ์ œ๋Š” STZ (100%)

์™€ TC (100%) ์˜€์œผ๋ฉฐ ๋‹ค์Œ์œผ๋กœ๋Š” OTC (75%)์™€ CTC (12.5%) ์ˆœ์œผ๋กœ ๊ฒ€์ถœ ๋นˆ๋„๊ฐ€ ๋†’์•˜๋‹ค (Table 7). ์„คํฐ์•„๋งˆ์ด๋“œ

๊ณ„์—ด ํ•ญ์ƒ์ œ ์ค‘ SMZ์™€ SMX๋Š” ๋ชจ๋“  ์ž‘๋ฌผ์ฒด ๋‚ด์—์„œ ๊ฒ€์ถœ๋˜์ง€ ์•Š์•˜๋‹ค. SMX์˜ ๊ฒฝ์šฐ ๋ชจ๋“  ํ† ์–‘ ์‹œ๋ฃŒ์—์„œ ํ•ญ์ƒ์ œ๊ฐ€ ๊ฒ€

์ถœ๋œ ๋ฐ˜๋ฉด ์ž‘๋ฌผ์ฒด ๋‚ด์—์„œ๋Š” ๊ฒ€์ถœ์ด ๋˜์ง€ ์•Š์•˜์œผ๋ฉฐ SMZ ์—ญ์‹œ ์ด 8์ง€์  ์ค‘ 4์ง€์ ์˜ ํ† ์–‘์—์„œ ๊ฒ€์ถœ๋œ ๋ฐ˜๋ฉด ์ž‘๋ฌผ์ฒด ๋‚ด์—

์„œ๋Š” ๊ฒ€์ถœ ๋˜์ง€ ์•Š์•˜๋‹ค.

ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด ํ•ญ์ƒ์ œ์˜ ์ž‘๋ฌผ ์ถ•์  ๋†๋„ ๋ฒ”์œ„๋Š” 5.1 - 194.0 ยตg kg-1์ด์˜€์œผ๋ฉฐ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด ํ•ญ์ƒ์ œ์˜

์ž‘๋ฌผ์ฒด ๋‚ด ๋†๋„ ๋ฒ”์œ„๋Š” 24.9 - 36.3 ยตg kg-1์ด์—ˆ๋‹ค. ๋‘ ๊ณ„์—ด์˜ ํ•ญ์ƒ์ œ๋ฅผ ๋น„๊ตํ•˜์˜€์„ ๊ฒฝ์šฐ ๊ฒ€์ถœ๋นˆ๋„์™€ ๊ฒ€์ถœ ๋†๋„ ๋ชจ๋‘ ํ…Œ

ํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด ํ•ญ์ƒ์ œ๊ฐ€ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด ํ•ญ์ƒ์ œ๋ณด๋‹ค ๋†’์•˜๋‹ค.

์ž‘๋ฌผ์ฒด ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ๋Š” ์ฃผ๋กœ ํ‡ด๋น„์— ์ž”๋ฅ˜๋˜์–ด ์žˆ๋Š” ํ•ญ์ƒ์ œ๊ฐ€ ํ† ์–‘์— ์œ ์ถœ๋œ ํ›„ ์ž‘๋ฌผ์ฒด๋กœ ์ „์ด๋˜๋Š” ๊ฒฝ๋กœ์ด๋‹ค (Pan

and Chu, 2017). ์„ ํ–‰์—ฐ๊ตฌ์— ์˜ํ•˜๋ฉด ์ž‘๋ฌผ์ฒด ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ์˜ ๋†๋„๋Š” Kow ๋ณ€์ˆ˜ ๊ฐ’๊ณผ ์ƒ๊ด€ ๊ด€๊ณ„๋ฅผ ๊ฐ€์ง€๋ฉฐ Kow๊ฐ€ ๋‚ฎ

์€ ์นœ์ˆ˜์„ฑ ํ•ญ์ƒ์ œ์˜ ๊ฒฝ์šฐ ์†Œ์ˆ˜์„ฑ ํ•ญ์ƒ์ œ์— ๋น„ํ•ด ์ž‘๋ฌผ ์ „์ด ํ™•๋ฅ ์ด ๋†’์•˜๋‹ค (Wu et. al., 2013). ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด

ํ•ญ์ƒ์ œ์˜ ์ž‘๋ฌผ ๋‚ด ์ถ•์  ๋†๋„๋Š” 5.6 - 532.0 ยตg kg-1์ด๋ฉฐ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด ํ•ญ์ƒ์ œ๋Š” 2.70 - 4.20 ยตg kg

-1์˜ ์ž‘๋ฌผ ๋‚ด ์ถ•

์  ๋ฒ”์œ„๋ฅผ ๋‚˜ํƒ€๋ƒˆ๋‹ค (Pan and Chu, 2017). ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ๊ณผ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด ํ•ญ์ƒ์ œ์˜ Kow ๊ฐ’์„ ๋น„๊ตํ•˜์˜€์„

๊ฒฝ์šฐ ์„คํฐ์•„๋งˆ์ด๋“œ์˜ pH ์กฐ์ • Kow ๊ฐ’์€ -1.5 - 1.0 ๋ฒ”์œ„์˜€์œผ๋ฉฐ ํ…ŒํŠธ๋ผ์‚ฌ์ดํด๋ผ์ธ ๊ณ„์—ด ํ•ญ์ƒ์ œ์˜ ๊ฒฝ์šฐ pH์กฐ์ • Kow

๊ฐ’์€ -5.0 ~ -3.0์œผ๋กœ ์„คํฐ์•„๋งˆ์ด๋“œ์— ๋น„ํ•ด ์นœ์ˆ˜์„ฑ์˜ ํŠน์„ฑ์„ ๊ฐ€์ง€๊ณ  ์žˆ์–ด ๋ณด๋‹ค ๋†’์€ ์ž‘๋ฌผ ๋‚ด ์ถ•์  ๋†๋„๋ฅผ ๋‚˜ํƒ€๋ƒˆ๋‹ค

(Pan and Chu, 2017). ๋˜ํ•œ ์„คํฐ์•„๋งˆ์ด๋“œ ๊ณ„์—ด ํ•ญ์ƒ์ œ๋Š” ์ค‘์„ฑ์กฐ๊ฑด์—์„œ ์Œ์ด์˜จ์œผ๋กœ ์กด์žฌํ•˜๋ฉฐ ์ค‘์„ฑ์กฐ๊ฑด (pH 7.2)์„ ๊ฐ€

์ง„ ์„ธํฌ์งˆ์„ ํ†ต๊ณผํ•˜๋Š” ๊ณผ์ •์—์„œ ์„ธํฌ๋ง‰ ๋˜๋Š” ์„ธํฌ๋ฒฝ ์‚ฌ์ด์— ํก์ฐฉ๋˜์–ด ์ž‘๋ฌผ ์ „์ด๊ฐ€ ๋‚ฎ๊ฒŒ ๋œ๋‹ค (Edginaton, 1981).

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Monitoring of Veterinary Antibiotics in the Agro-Environment โˆ™ 587

Conclusion

๋†์ดŒ ํ™˜๊ฒฝ ๋‚ด ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด ๋‚ด ํ•ญ์ƒ์ œ ์ž”๋ฅ˜๋Ÿ‰์„ ๋ชจ๋‹ˆํ„ฐ๋งํ•˜์˜€๋‹ค. ํ† ์–‘๊ณผ ์ž‘๋ฌผ์ฒด ๋ชจ๋‘ Mcllvaine ์™„์ถฉ์šฉ์•ก์„ ์ด์šฉ

ํ•˜์—ฌ ์ถ”์ถœํ•˜์˜€์œผ๋ฉฐ ๊ณ ํ˜•์ƒ ์ถ”์ถœ๋ฒ•์œผ๋กœ ์ •์ œ ํ›„ ์•ก์ฒดํฌ๋กœ๋งˆํ† ๊ทธ๋ž˜ํ”ผ ํƒ„๋ค ์งˆ๋Ÿ‰ ๋ถ„์„๊ธฐ (HPLC/MS/MS)๋ฅผ ์ด์šฉํ•˜์—ฌ

์ž”๋ฅ˜ ํ•ญ์ƒ์ œ๋ฅผ ๋ถ„์„ํ•˜์˜€๋‹ค. ๋ถ„์„ ๊ฒฐ๊ณผ ํ† ์–‘ ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ๋Š” TC์™€ SA ๊ณ„์—ด์ด ๊ฐ๊ฐ 0.58 - 3.34, 0.12 - 3.02 ยตg kg-1

์ˆ˜

์ค€์œผ๋กœ ๊ฒ€์ถœ๋˜์—ˆ์œผ๋ฉฐ ์ž‘๋ฌผ์ฒด ๋‚ด TC์™€ SA ๊ณ„์—ด ํ•ญ์ƒ์ œ๋Š” 15.1 - 194.0, 24.9 - 36.3 ยตg kg-1

์ˆ˜์ค€์œผ๋กœ ๊ฒ€์ถœ๋˜์—ˆ๋‹ค. ํ† ์–‘

๊ณผ ์ž‘๋ฌผ์ฒด์— ์ž”๋ฅ˜ํ•˜๋Š” ํ•ญ์ƒ์ œ๋Š” ํ•ญ์ƒ์ œ ํŠน์„ฑ๊ณผ ํ† ์–‘์˜ ํ™”ํ•™์  ํŠน์„ฑ์— ๋”ฐ๋ผ ์ž”๋ฅ˜ ์–‘์ƒ์ด ๋‹ค๋ฆ„์„ ์•Œ์•˜์œผ๋ฉฐ ํ–ฅํ›„ ํ•ญ์ƒ์ œ

์˜ ํ™˜๊ฒฝ ์œ ์ถœ ์›์ธ์ธ ํ‡ด๋น„ ๋ฐ ์•ก๋น„์™€ ๊ฐ™์€ ๋ถ€์‚ฐ๋ฌผ ๋น„๋ฃŒ ๋‚ด ์ž”๋ฅ˜ ํ•ญ์ƒ์ œ ๋ชจ๋‹ˆํ„ฐ๋ง์ด ํ•„์š”ํ•  ๊ฒƒ์œผ๋กœ ์‚ฌ๋ฃŒ๋œ๋‹ค.

Acknowledgement

We gratefully acknowledge the financial support of โ€œproject No. 01336702โ€ by Rural Development Administration,

Republic of Korea.

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