본 연구는 농약 허용물질목록관리제도(PLS) 도입이 농산물 중 잔류농약 부적합에 어떠한 영향을 미쳤는지 확인 하기 위해 2018년부터 2020년까지 서울 강서지역에서 유통되는 농산물을 대상으로 잔류농약을 검사하였다. 농산물 8,081건을 대상으로 340종의 동시분석 농약에 대해 GCMS/ MS, GC-MSD, HPLC-MS/MS를 이용하여 분석하였고, 부적합 농산물은 2018년 67건(2.5%), 2019년 49건(1.9%), 2020년 39건(1.4%)으로 나타났다. PLS제도 도입 전과 도입 후의 잔류농약 부적합 증감효과를 알아보기 위해 카이 제곱 검정을 통한 교차분석 결과에서 χ2=8.383, P=0.015 (95% 신뢰수준)를 나타내어 PLS 제도 도입 후에 부적합률이 유의하게 감소함을 알 수 있었다.

전국 12개 지역에서 수집된 표고 768건, 표고배지 143 건의 시료를 대상으로 다종다성분 320종 및 단성분 mepiquat chloride에 대해 분석한 결과, 표고 4건, 표고배지 3건으로 총 7건에서 잔류농약이 검출되었으며, 검출된 성분은 carbendazim, diflubenzuron, fluopyram, dinotefuran 이었다. 본 연구에서는 표고 3건, 배지 1건으로 총 4건의 시료에서 carbendazim이 검출되었으나 각각의 검출량은 0.056 mg/kg, 0.17 mg/kg, 0.043 mg/kg, 0.09 mg/kg으로 MRL 인 0.7 mg/kg에 비해 소량으로 나타났다. Fluopyram은 0.068 mg/kg, dinotefuran은 0.06 mg/kg으로 모두 배지에서 각각 1건씩 검출되었다. 식물생장조절제로 사용되는 mepiquat chloride는 본 연구에서는 검출되지 않았다. 전체 수집표고 중 소수의 시료에서 잔류농약이 검출되었나, 등록되지 않은 농약은 PLS에 의하면 0.01 ppm이 최대허용치로 구분되어 있어, 후속 연구를 통하여 표고를 비롯한 버섯류의 안전성의 기준 작성에 필수적인 자료를 확보하고자 한다.

This study was conducted to evaluate the degradation and mineralization of PPCPs (Pharmaceuticals and Personal Care Products) using a CBD(Collimated Beam Device) of UV/H2O2 advanced oxidation process. The decomposition rate of each substance was regarded as the first reaction rate to the ultraviolet irradiation dose. The decomposition rate constants for PPCPs were determined by the concentration of hydrogen peroxide and ultraviolet irradiation intensity. If the decomposition rate constant is large, the PPCPs concentration decreases rapidly. According to the decomposition rate constant, chlortetracycline and sulfamethoxazole are expected to be sufficiently removed by UV irradiation only without the addition of hydrogen peroxide. In the case of carbamazepine, however, very high UV dose was required in the absence of hydrogen peroxide. Other PPCPs required an appropriate concentration of hydrogen peroxide and ultraviolet irradiation intensity. The UV dose required to remove 90% of each PPCPs using the degradation rate constant can be calculated according to the concentration of hydrogen peroxide in each sample. Using this reaction rate, the optimum UV dose and hydrogen peroxide concentration for achieving the target removal rate can be obtained by the target PPCPs and water properties. It can be a necessary data to establish design and operating conditions such as UV lamp type, quantity and hydrogen peroxide concentration depending on the residence time for the most economical operation.

In this study, the fate and removal of 15 pharmaceuticals (including stimulants, non-steroidal anti-inflammatory drugs, antibiotics, etc.) in unit processes of a sewage treatment plant (STP) were investigated. Mass loads of pharmaceuticals were 2,598 g/d in the influent, 2,745 g/d in the primary effluent, 143 g/d in the secondary effluent, and 134 g/d in the effluent. The mass loads were reduced by 95% in the biological treatment process, but total phosphorous treatment did not show a significant effect on the removal of most pharmaceuticals. Also, mass balance analysis was performed to evaluate removal characteristics of pharmaceuticals in the biological treatment process. Acetaminophen, caffeine, acetylsalicylic acid, cefradine, and naproxen were efficiently removed in the biological treatment process mainly due to biodegradation. Removal efficiencies of gemfibrozil, ofloxacin, and ciprofloxacin were not high, but their removal was related to sorption onto sludge. This study provides useful information on understanding removal characteristics of pharmaceuticals in unit processes in the STP.

The aim of this study was to evaluate pretreatment methods for 27 pharmaceuticals and personal care products (PPCPs) in various sewage samples using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) and online solid-phase extraction with LC-MS/MS. Extraction efficiencies of PPCPs in the solid phase under different experimental conditions were evaluated, showing that the highest recoveries were obtained with the addition of sodium sulfate and ethylenediaminetetraacetic acid disodium salt dehydrate in acidified conditions. The recoveries of target compounds ranged from 91 to 117.2% for liquid samples and from 61.3 to 137.2% for solid samples, with a good precision. The methods under development were applied to sewage samples collected in two sewage treatment plants (STPs) to determine PPCPs in liquid and solid phases. Out of 27 PPCPs, more than 19 compounds were detected in liquid samples (i.e., influent and effluent) of two STPs, with concentration ranges of LOQ-33,152 ng/L in influents and LOQ-4,523 ng/L in effluents, respectively. In addition, some PPCPs such as acetylsalicylic acid, ibuprofen, and ofloxacin were detected at high concentrations in activated sludge as well as in excess sludge. This methodology was successfully applied to sewage samples for the determination of the target compounds in STPs.

액화석유가스(Liquefied Petroleum Gas)를 연료(Fuel)로 하는 차량의 실제 운행단계에서 시동 꺼짐 현상 등이 발생한다는 소비자 민원이 접수 된 바 있으며, 최근 유통과정에서 녹 등의 이물질로 인한 소비자 피해 가능성이 제기되어 LPG 잔류물질(Residue) 항목에 대한 관리 필요성이 대두되었다. 본 연구에서는 LPG 국내생산 및 수입사 제품과 실제로 유통되고 있는 LPG의 잔류물질 특성을 연구하였다. LPG 잔류물질을 GC-MS를 사용하여 정성분석을 하였고, ICP-OES를 이용하여 무기물 성분을 분석하였다. GC-MS 분석결과 고무 제조공정을 용이하게 하기 위해 고무에 소량 배합하는 가소제(Plasticizer) 등이 분석되었다. 또한 ICP-OES를 이용한 무기물 분석결과 주로 LPG 생산 시 사용되는 소포제 등에서 유래된 것으로 추정되는 Si와 충전시설 등에 사용되는 그리스 첨가제 성분 등으로 추정되는 P와 Zn도 일부 검출되었다. 본 연구에서 분석된 LPG 잔류물질에 대해서는 녹 등을 유발할 수 있는 성분이 검출되지 않았지만 가소제 및 그리스 첨가제 성분이 LPG 연료계통에 영향을 줄 수 있으므로 적정품질의 고무류 사용과 저비점 그리스 첨가제 사용 확대가 필요할 것으로 보인다.

Oxidation of erythromycin, sulfamethazine and sulfathiazole by ozone was experimentally investigated to see the effects of background water quality such as ultrapure water, humic acid and biologically treated wastewater and water temperature on the removal rate, consequently to provide design information when the ozone treatment process is adopted. Initial concentration of the antibiotics was spiked to 10 μg/l and ozone dose was 1, 2, 3, 5, 8 mg/l. While the removal rate of erythromycin under ultrapure water background by ozone oxidation was over 99%, that under humic acid and biologically treated wastewater background was markedly reduced to the range of 59.8%~99% and 17.0%~99%, respectively. When water temperature is decreased from 20℃ to 4℃, the removal rate is reduced from the range of 17.0%~99% to the range of 9.4%~97.4% under biologically treated wastewater background. The effects of background and temperature on the removal rate of sulfamethazine and sulfathiazole were similar to erythromycin, but the degree was different. Therefore, it is concluded that the background of water to be treated as well as water temperature should be taken into consideration when the design factor such as ozone dose is determined to meet the treatment objective in the ozone treatment process.

Study on effluent organic matter (EfOM) characteristic and removal efficiency is required, because EfOM is important in regard to the stability of effluents reuse, quality issues of artificial recharge and water conservation of aqueous system. UV technology is widely used in wastewater treatment. Many reports have been conducted on microbial disinfection and micro pollutant reduction with UV treatment. However, the study on EfOM with UV has limited because low/medium pressure UV lamp is not sufficient to affect refractory organics. The high intensity of pulsed UV would mineralize EfOM itself as well as change the characteristics of EfOM. Chlorine demand and DBPs formation is affected on the changed amounts and properties of EfOM. The objective of this study is to investigate the effect on EfOM, chlorine residual, and chlorinated DBPs formation with low pressure and pulsed UV treatment. The removal of organic matter through low pressure UV treatment is insignificant effect. Pulsed UV treatment effectively removes/transforms EfOM. As a result, the chlorine consumption is changed and chlorine DBPs formation is decreased. However, excessive UV treatment caused problems of increasing chlorine consumption and generating unknown by-products.

Cosmetics using natural materials which was purchased in retail stores, distributed in Gyeonggi province(32 samples) and online through internet(24 samples) were analyzed by pesticide residues and target preservatives for assessing the safety of it. Natural or organic certifications was identified in 22 samples among 56 samples and most of them were Ecocert. Pesticide residues was detected in 3 samples among 56 samples and each compound and concentration was permethrin(0.6 mg/kg), tricyclazole(11.7 mg/kg) and malathion(0.05 mg/kg). All of it was purchased through internet. Target preservatives was detected in 13 samples among 56 samples and one of them was over the maximum allowed concentration and the rest of them were within the maximum allowed concentration of the respective preservatives. The compound which was over the maximum allowed concentration was benzoic acid and compounds which were within the maximum allowed concentration were sorbic acid, benzoic acid and methylparaben. They were all identified substances in products and the number of detected preservatives in retail stores were higher than online samples purchased through internet. As a result of this study, The method of analyzing pesticide residues and limit in cosmetics using natural materials should be set up as soon as possible and the monitoring about preservatives in cosmetics using natural materials should be conducted on continuously.

A rapid, simple and reliable LC-MS/MS method, which can be used on a routine basis, was developed for the simultaneous detection of 8 penicillin antibiotics (amoxicillin, ampicillin, penicillin-G, penicillin-V, oxacillin, cloxacillin, nafcillin and dicloxacillin) in swine muscle and kidney. The antibiotics were extracted from samples with water and methanol. The extract was centrifuged, filtered and analyzed by liquid chromatography coupled with a tandem mass spectrometer (LC-MS/MS), using a C18 reversed phase column with water/acetonitrile gradient containing 0.05 % formic acid. Mass spectral acquisition was achieved in an electrospray positive ion mode by applying multiple reaction monitoring (MRM) of 2 fragment ion transitions to provide a high degree of sensitivity and specificity. The ion rations were consistent and could be used for confirmation of identity of the penicillin antibiotics. Recoveries of eight penicillins at three fortification levels (10, 20 and 40㎍/㎏) ranged from 79.8 to 102.4% and 72.8 to 103.4% in swine muscle and kidney, respectively. The coefficient of variation was than 9% in all samples. The estimated limits of quantification (LOQs) ranged from 1.0 to 3.2㎍/㎏ in swine muscle and kidney, respectively. The LOQs of this method are below the MRLs of penicillin antibiotics in animal tissues established in Korea and other countries.

This study was conducted to investigate the residue amount of harmful materials on the 153 commercial medical herbs in Gwangju area. It was performed using the GC-ECD, GC-NPD, GC-MSD and the LC-UVD,LC-FLD, LC-MSD to analyze 200 pesticides. The heavy metals were determined using a Mercury analyzer and AAS. The sulfur dioxides were analyzed by modified Monnier-Williams method. The residual pesticides were detected in 7samples, and were over MRLs (Maximum Risk Levels) in 2 samples (1.3%). The mean values of heavy metal contents (mg/kg) were Pb, 0.570; Cd, 0.081; As, 0.082; Hg, 0.0093. The measured values of Pb, As, Hg showed within MRLs. The excess samples of MRLs were 3 samples (changchul 2, cheongung 1) on Cd. The sulfur dioxides were over MRLs in 7 samples (4.6%), hwanggi and gugija. These results will be used to establish on the regulation of commercial medical herbs in Gwangju area.

잔류물질 간이 시험법으로 EEC-4 plate test와 Charm II test가 항생물질과 합성항균제 잔류검사에 널리 이용되고 있는 바, 이들 상호간의 결과 수치를 비교, 분석한 결과 다음과 같은 결론을 얻었다. EEC-4 plate 혹은 Charm II에서 양성으로 나타난 돈육 71건에 대하여 HPLC로 정량 분석한 결과, only tetracyclines 46건, only sulfonamides와 solfonamides+tetracyclines가 각각 4건씩, amphenicols+tetracyclines와 amphenicols+sulfonamides+tetracyclines가 각각 1건씩 검출되었고, 15건에서는 검출되지 않았다. Sulfonamides 계열에서 검출된 9건의 경우, Charm-II test 결과 수치가 낮은 경우에 정량 검출량이 높게 나타났고, EEC-4 plate test결과 pH6.0, pH7.2, pH8.0모두에서 양성으로 나타나는 등 두 시험방법 간에 연관성이 있었고, chloramphenicols 계열에서 검출된 2건과 검출되지 않은 7건의 경우, Charm-II test결과 수치가 낮은 경우에는 오히려 정량 검출되지 않았으나, control point근방의 양성 수치에서는 검출량이 높게 나타날 뿐 아니라 EEC-4 plate test에서도 pH 6.0, pH 7.2, pH 8.0 모두에서 양성으로 나타나는 등 두 시험방법 간에 연관성이 있었다. 한편, tetracycline 계열의 경우, EEC-4 plate와 Charm-II간에 연관성은 없었다. 또한, EEC-4 plate와 Charm II에서 각각 양성을 나타내었으나 HPLC에서는 검출되지 않는 경우는 tetracyclines계열에서는 10.5%(6/57), sulfonamides계열의 경우는 없었고, chloramphenicols계열의 경우는 81.8%(9/11)로 각각 나타나 EEC-4 plate와 Charm II가 세 가지 잔류물질 시험에 대한 screening method로서 적합함을 알 수 있었다.

1. 닭고기에서 4종의 플루오로퀴놀론계 합성항균제(ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin)를 액상추출법으로 추출하여 형광검출기와 HPLC를 이용하여 동시 정량분석하는 방법을 확립하였으며 분석조건으로서 컬럼은 Symmetry C18(250×4.6 mm id, 5 ㎛), 이동상은 0.4% triethylamine 및 0.4% phospholic acid 수용액, methanol 및 acetonitrile 혼합용액(800:100:100, v/v/v)을 사용하였으며, 형광검출기는 여기파장 278 nm, 측정파장 456 nm으로 그리고 유속은 1.0 ml/min., 주입량은 50 ㎕로 하였다. 확립된 분석조건으로 측정한 ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin 표준품의 표준곡선식에서 모두 상관계수 0.999이상의 양호한 직선성을 보였으며, 첨가한 닭고기의 크로마토그람에서도 각각의 nfwlfquf 분리시간대에 방해 피크 없이 양호한 분리도를 나타내었다. 0.05~0.2 ㎍/g 첨가한 시료에서 평균 회수율은 ofloxacin 92.0~95.4%, norfloxacin 84.2~87.3%, ciprofloxacin 78.3~82.2%, enrofloxacin 91.3~95.3%이었으며 변이계수(CV)는 2.7~9.4%이었다.4종의 동시분석법의 검출한계 및 정량한계는 각각 ofloxacin 23.5 ppb, 35.3 ppb, norfloxacin 3.4 ppb, 5.1 ppb, ciprofloxacin 3.0 ppb, 4.5 ppb, enrofloxacin 2.5 ppb, 3.8 ppb 수준이었다. 2. 인천 지역에서 돛구한 닭고기 총 1,523수를 EEC-4-plate법으로 검사한 결과 양성반응을 보인 닭고기는 15수(육계 10, 토종닭 5)였으며, HPLC를 이용한 정밀검사결과 육계 5수에서 ciprofloxacin이 불검출~0.04 ppm, enrofloxacin이 0.01~0.69 ppm수준으로 검출되었으며, 토종닭 5수에서는 ciprofloxacin이 0.02~0.12 ppm, enrofloxacin이 0.36~6.79 ppm수준으로 검출되었다.

A simple, rapid and simultaneous analytical method is described for the detection of Sulfonamide and Tetracycline residues, i.e., Sulfamerazine (SMR), Sulfamethazine (SMT), Sulfamonomethoxine (SMM), Sulfadimethoxine (SDM), Sulfaquinoxaline (SQN), Oxytetracycline (OXY), Tetracycline (TC), Chlortetracycline (CTC). Blank control and sulfonamide and tetracycline fortified fish muscle samples (0.5 g) were blended with octadecylsilyl (C,e, 40 gm, 21% load, 60Å) derivatized silica packing material (2 g). Blended fish samples were washed with hexane, then, benzene and dichloromethane were used for the elution of tetracycline and sulfonamide, respectively, The eluants containg tetracycline and sulfonamide were analyzed by HPLC. Correlation coefficients of standard curves for individual sulfonamide and tetracycline isolated from fortified samples were linear (0.9993±0.0003-0.9997±0.0003, 0.9493±0.078-0.9753±0.036), respectively, The average percentage recoveries of sulfonamide and tetracycline ranged as 80.86-96.52% to 85.88-92.23%, and 30.01-37.12% to 65.89-73.40%, for the concentration range (0.1--1.0 ppm) examined, respectively. Limit of detection for sulfonamide was 0. 05 ug/g, then, tetracycline was 0.1 ug/g. Detection of quantitation of sulfonamide residue was 0.0012 ppm for SMR in Paralichthys Odiuacleus and 0.0020 ppm for SMR, 0.015 ppm for SMM in Cyprinus Carpio. The applicability of this procedure is demonstrated by separation and detection of incurred tetracycline and sulfonamide residues in fish muscle tissue.