Sorption of pharmaceuticals to soil organic matter in a constructed wetland by electrostatic interaction

Park, Jongkwan,Cho, Kyung Hwa,Lee, Eunkyung,Lee, Sungyun,Cho, Jaeweon Elsevier 2018 Science of the Total Environment Vol.635 No.-

<P><B>Abstract</B></P> <P>There is a growing interest in the removal of pharmaceuticals from wastewater because pharmaceuticals have potential ecotoxicological effects. Among several removal mechanisms, the sorption of pharmaceuticals to sediment organic matter is an important mechanism related to the mobility of pharmaceuticals. This study investigated the sorption of pharmaceuticals to soil organic matter (SOM) by electrostatic interactions. SOM located on the surface of soil/sediment generally has a negative charge because of the functional groups present (i.e., carboxylic and phenolic groups). Thus, the electrical characteristics of SOM can induce electrical attraction with positively charged chemical compounds. In this study, SOM was extracted from soils under different aquatic plants (<I>Acorus</I> and <I>Typha</I>) in a constructed wetland in Korea. Experiments were carried out with the following three pharmaceuticals with different electrical characteristics at pH 7: atenolol (positive charge; pKa 9.5), carbamazepine (neutral; no pKa), and ibuprofen (negative charge; pKa 4.9). The SOM in the <I>Acorus</I> pond had a higher hydrophobicity and electrical charge density than that in the <I>Typha</I> pond. Regarding the sorption efficiency between SOM and charged pharmaceuticals, atenolol showed highest sorption efficiency (~60%), followed by carbamazepine (~40%) and ibuprofen (<~30%). In addition, the removal efficiency of the targeted pharmaceuticals in the constructed wetland was estimated by comparing the concentrations of the pharmaceuticals at sampling points with flowing water. The results showed that the removal efficiency of atenolol and carbamazepine was almost 50%, whereas that of ibuprofen was only ~10%. A comparison of the results of lab-scale and field experiments showed that electrostatic interaction is one of the major pharmaceutical removal mechanisms in a constructed wetland.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Sorption of pharmaceuticals to SOM by electrostatic interaction is studied. </LI> <LI> SOM was sampled from soils under aquatic plants <I>Acorus</I> and <I>Typha</I> in a wetland. </LI> <LI> The experiments used three pharmaceuticals: atenolol, carbamazepine, and ibuprofen. </LI> <LI> Atenolol had highest sorption efficiency, followed by carbamazepine and ibuprofen. </LI> <LI> Electrostatic interaction is a major removal mechanism in constructed wetlands. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

낙동강 하류 정수장을 대상으로 모의 오존 및 자외선/과산화수소 공정을 이용한 의약물질 제거능 및 예측모델 평가

서창동(Chang-Dong Seo),이우림(Woorim Lee),염훈식(Hoon-Sik Yoom),최상기(Sangki Choi),이윤호(Yunho Lee),손희종(Heejong Son) 대한환경공학회 2021 대한환경공학회지 Vol.43 No.7

목적: 낙동강 하류에 위치한 대형 정수장으로 유입 가능성이 높은 의약물질들에 대해 후 오존(O₃) 공정에서의 제거능과 후O₃ 처리공정을 대체할 수 있는 자외선/과산화수소(UV/H₂O₂) 공정에서의 제거능을 함께 평가하고, 이들 공정에서 의약물질들에 대한 제거율 예측 모델을 사용하여 수질변화에 따른 제거율 예측을 수행하여 정수장 선진화 사업의 자료로 활용하고자 하였다. 방법: 낙동강 하류 정수장의 모래여과수를 대상으로 19종의 의약물질들에 대하여 O₃ 및 UV/H₂O₂ 처리를 진행하였다. 순수 및 모래 여과수에서의 제거율 평가를 위하여 의약물질 19종을 각각 100 ng/L 농도로 투입하였다. O₃ 처리실험에서 O₃ 주입량은 0.1∼2.0 gO₃/gDOC (0.25∼5.0 mgO₃/L)의 범위였으며, UV/H₂O₂ 공정에서는 시료에 H₂O₂ (5, 10 mg/L)를 투입하여 0∼1,500 mJ/cm²의 범위로 UV을 조사하였다. 결과 및 토의 : 후O₃ 공정을 모사한 O₃ 처리실험의 경우, O₃ 주입량 0.2 gO₃/gDOC (=0.5 mgO₃/L) 조건에서 O₃과 높은 반응성(kO₃ 6.5×10²∼2.6×10<SUP>6</SUP> M<SUP>-1</SUP> s<SUP>-1</SUP>)을 가진 17종의 의약물질들은 92% 이상 제거되었다. 그러나 iopromide (IPM)와 primidione (PRM) 2종은 O₃과의 낮은 반응성(kO₃ < 1 M<SUP>-1</SUP> s<SUP>-1</SUP>)으로 인하여 동일한 O₃ 입량(0.2 gO₃/gDOC)조건에서 36∼45% 정도의 저조한 제거율을 나타내었다. IPM과 PRM에 대해 90% 이상의 제거율을 얻기 위해서는 2.0 gO₃/gDOC 이상의 O₃ 주입량이 요구되어 O₃ 처리만으로는 제어가 어려운 것으로 평가되었다. H₂O₂ 투입농도 10 mg/L, UV 조사량 500과 1,000 mJ/cm²의 조건으로 UV/H₂O₂ 공정을 모사한 경우, 19종의 의약물질 제거율은 각각 63∼99% 및 87∼99%였으며, caffeine (CAF)의 제거율이 가장 낮았다. O₃ 공정에서 제거율이 낮은 IPM 및 PRM의 경우에는 OH 라디칼과의 빠른 반응속도(kOH = 3.3×10<SUP>9</SUP> 및 5.2×10<SUP>9</SUP> M<SUP>-1</SUP> s<SUP>-1</SUP>)로 인하여 O₃ 공정에 비하여 제거율이 높은 것으로 평가되었다. O₃ 및 UV/H₂O₂ 공정에서 수중의 용존 유기물질 농도변화에 따른 의약물질들의 제거율 변화를 평가하기 위해 화학적 동역학 모델을 사용하여 제거율 예측모델을 적용해 본 결과, 용존성 유기물질농도가 1.5 mg/L에서 3.0 mg/L로 증가할 경우 O₃ 공정(O₃ 투입농도 1.0과 2.0 mg/L)에서의 IPM과 PRM은 각각 22∼24% 및 15∼24% 정도 제거율이 감소하였다. 또한, UV/H₂O₂ 공정(H₂O₂ : 10 mg/L, UV : 500∼1,000 mJ/cm²)의 경우에는 용존 유기물질 농도가 1.5∼3.0 mg/L로 증가하였을 때 16종의 의약물질들의 제거율이 0∼29% 정도 감소되었으며, CFN의 제거율 감소폭이 가장 높게 나타났다 결론: O₃ 및 UV/H₂O₂ 처리공정에 의한 의약물질 제거율 평가 및 예측을 진행한 결과, 의약물질류 제거를 위해 O₃ 공정의 대체공정으로 UV/H₂O₂ 공정의 적용 가능성을 확인하였다. Objectives : In the case of pharmaceuticals with high possibility of inflow into the large drinking water treatment plant (DWTP) located in the downstream of the Nakdong River, we tried to evaluate the removal efficiency of pharmaceuticals in the both ozone (O₃) and the UV/H₂O₂ treatment as an alternative of post-O₃ process. It was intended to be used as data for the advanced WTP project by prediction of the removal efficiency in the O₃ and UV/H₂O₂ processes with varying water quality conditions. Methods : O₃ and UV/H₂O₂ process were performed for 19 kinds of pharmaceuticals in the sand-filtered water of DWTP. In order to evaluate the removal efficiency in deionized water (DI) and sand-filtered water (SFW) matrices, 19 pharmaceuticals were spiked at a concentration of 100 ng/L, respectively. In the O₃ process, the specific O₃ dose was 0.1∼2.0 gO₃/gDOC (0.25∼5.0 mgO₃/L). In the UV/H₂O₂ process, H₂O₂ (5 and 10 mg/L) was added to the sample before UV was irradiated (0∼1,500 mJ/cm²). Results and Discussion : In the case of simulated post-O₃ process, the removal efficiency of high-ozone reactive pharmaceuticals (kO₃ 6.5×10²∼2.6×10<SUP>6</SUP> M<SUP>-1</SUP> s<SUP>-1</SUP>) was up to 92% at the specific O₃ dose of 0.2 gO₃/gDOC. However, the removal efficiency of iopromide (IPM) and primidone (PRM) was only 36∼45% in the same O₃ dose (0.2gO₃/gDOC) due to the low O₃ reactivity (kO₃ < 1 M<SUP>-1</SUP> s<SUP>-1</SUP>). A specific O₃ dose of 2.0 gO₃/gDOC (=5 mgO₃/L) was required to achieve a removal efficiency of over 90% for IPM and PRM, indicating that these O₃-refractory pharmaceuticals are difficult to control by O₃ process. In the case of simulated UV/H₂O₂ (10 mg/L H₂O₂) process, the removal efficiency of 19 pharmaceuticals at the UV fluence of 500 and 1,000 mJ/cm² were 63∼99% and 87∼ 99%, respectively, and caffeine (CFN) had the lowest removal efficiency. For the O₃-refractory pharmaceuticals (i.e., IPM and PRM), the removal efficiency was higher in the UV/H₂O₂ process than that in the O₃ process due to the high reactivity with OH radical (kOH = 3.3×10<SUP>9</SUP> and 5.2×10<SUP>9</SUP> M<SUP>-1</SUP> s<SUP>-1</SUP>). Prediction of removal efficiency for pharmaceuticals in the O₃ and UV/H₂O₂ process was performed using chemical kinetics model to evaluate the change in removal efficiency with varying DOM concentration. As a result of prediction model for O₃, when the DOM concentration increased from 1.5 to 3.0 mg/L, the removal efficiency of IPM and PRM decreased by 22∼ 24% and 15∼24%, respectively. In the case of UV/H₂O₂ process (10 mg/L H₂O₂ and UV fluence of 500~1,000 mJ/cm²), the removal efficiency of 16 kinds of pharmaceuticals was reduced by 0∼29%, and the degree of reduction in the removal efficiency of CFN was the highest. Conclusions : As a result of evaluation and prediction of the removal efficiency of pharmaceuticals in the O₃ and UV/H₂O₂ treatment processes, it is confirmed that the possibility of applying the UV/H₂O₂ treatment as an alternative process to the O₃ to abatement of pharmaceuticals.

Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15

Bui, Tung Xuan,Pham, Viet Hung,Le, Son Thanh,Choi, Heechul Elsevier 2013 Journal of hazardous materials Vol.254 No.-

<P><B>Abstract</B></P> <P>The adsorption of a complex mixture of 12 selected pharmaceuticals to trimethylsilylated mesoporous SBA-15 (TMS-SBA-15) has been investigated by batch adsorption experiments. The adsorption of pharmaceuticals to TMS-SBA-15 was highly dependent on the solution pH and pharmaceutical properties (i.e., hydrophobicity (log <I>K</I> <SUB>ow</SUB>) and acidity (p<I>K</I> <SUB>a</SUB>)). Good log–log linear relationships between the adsorption (<I>K</I> <SUB>d</SUB>) and pH-dependent octanol–water coefficients ( K ow pH ) were then established among the neutral, anionic, and cationic compounds, suggesting hydrophobic interaction as a primary driving force in the adsorption. In addition, the neutral species of each compound accounted for a major contribution to the overall compound adsorption onto TMS-SBA-15. The adsorption kinetics of pharmaceuticals was evaluated by the nonlinear first-order and pseudo-second-order models. The first-order model gave a better fit for five pharmaceuticals with lower adsorption capacity, whereas the pseudo-second-order model fitted better for seven pharmaceuticals having higher adsorption capacity. In the same group of properties, pharmaceuticals having higher adsorption capacity exhibited faster adsorption rates. The rate-limiting steps for adsorption of pharmaceuticals onto TMS-SBA-15 are boundary layer diffusion and intraparticle diffusion including diffusion in mesopores and micropores. In addition, the adsorption of pharmaceuticals to TMS-SBA-15 was not influenced by the change of initial pharmaceutical concentration (10–100μgL<SUP>−1</SUP>) and the presence of natural organic matter.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Trimethylsilylated SBA-15 for adsorptive removal of a mixture of 12 pharmaceuticals. </LI> <LI> Hydrophobic interaction as a primary driving force in the adsorption. </LI> <LI> The rate-limiting steps were diffusion through boundary layer, mesopores and micropores. </LI> <LI> Adsorption efficiency was not changed as pharmaceutical concentration varied. </LI> <LI> Adsorption efficiency was not influenced by the presence of natural organic matters. </LI> </UL> </P>

PhATETM 모형을 적용한 금강수계 중 의약물질 농도 추정

임득순,박정임 한국환경보건학회 2009 한국환경보건학회지 Vol.35 No.1

In recent years, pharmaceuticals in the aquatic environment have become a matter of increasing public concern. Environmental risk assessment (ERA), including an exposure assessment, is considered the best scientifically based approach for evaluating the potential effects of pharmaceuticals on ecosystems. Computerized exposure models constitute an important tool in predicting environmental exposures of pharmaceuticals. This paper presents the applicability of an exposure model by comparing measured data of selected pharmaceuticals with predicted environmental concentrations from an exposure model. PhATETM (Pharmaceutical Assessment and Transport Evaluation) model developed by the Pharmaceutical Research and Manufacturers of America (PhRMA) was adapted to run simulations for the Keum River. A set of 7 pharmaceuticals of high production in Korea was modeled. The PECs generated by the PhATETM model that were then compared to the measured concentrations. The PhATETM model predicted concentrations for 7 pharmaceuticals including acetaminophen, acetylsalicylic acid, erythromycin, ibuprofen, lincomycin, mefenamic acid, and naproxen were in good agreement with actual measured concentrations, which demonstrated the utility of PhATETM as a predictive tool. In conclusion, PhATETM, although it does not intend to accurately represent reality, could be utilized for rapid predictions of the environmental concentrations of pharmaceuticals.

PhATE^TM 모형을 적용한 금강수계 중 의약물질 농도 추정

임득순,박정임,Lim, Deuck-Soon,Park, Jeong-Im 한국환경보건학회 2009 한국환경보건학회지 Vol.35 No.1

In recent years, pharmaceuticals in the aquatic environment have become a matter of increasing public concern. Environmental risk assessment (ERA), including an exposure assessment, is considered the best scientifically based approach for evaluating the potential effects of pharmaceuticals on ecosystems. Computerized exposure models constitute an important tool in predicting environmental exposures of pharmaceuticals. This paper presents the applicability of an exposure model by comparing measured data of selected pharmaceuticals with predicted environmental concentrations from an exposure model. $PhATE^{TM}$ (Pharmaceutical Assessment and Transport Evaluation) model developed by the Pharmaceutical Research and Manufacturers of America (PhRMA) was adapted to run simulations for the Keum River. A set of 7 pharmaceuticals of high production in Korea was modeled. The PECs generated by the $PhATE^{TM}$ model that were then compared to the measured concentrations. The $PhATE^{TM}$ model predicted concentrations for 7 pharmaceuticals including acetaminophen, acetylsalicylic acid, erythromycin, ibuprofen, lincomycin, mefenamic acid, and naproxen were in good agreement with actual measured concentrations, which demonstrated the utility of $PhATE^{TM}$ as a predictive tool. In conclusion, $PhATE^{TM}$, although it does not intend to accurately represent reality, could be utilized for rapid predictions of the environmental concentrations of pharmaceuticals.

PhATE™ 모형을 적용한 금강수계 중 의약물질 농도 추정

임득순(Deucksoon Lim),박정임(Jeongim Park) 한국환경보건학회 2009 한국환경보건학회지 Vol.35 No.1

In reεent years, pharmaceuticals in the aquatic environment have become a matter of increasing public concεm. Environmental sk assessment (ERA), including an exposure assessment, is considered the best scientifically basεd approach for evaluating the potential effects of pharmaceuticals on ecosystεms. Computerized exposure models constitute an important tool in predicting environmental exposures of pharmaceuticals. This papεr presents the applicability of an exposure model by comparing measured data of selected pharmaceuticals with predicted environmental concentrations from an exposure model. PhATE™ (Pharmaceutical Assessment and Transport Evaluation) model developed by the Pharmaceutical Research and Manufacturers of America (PhRMA) was adapted to run simulations for the Keum River. A set of 7 pharmaceuticals of high production in Korea was modeled. The PECs generated by the PhATE1M model that were then compared to the measured concentrations. The PhATE7M model predicted concεntrations for 7 pharmaceuticals including acεtarninophen, acetylsalicylic acid, erythromycin, ibuproflεn, lincomycin, mefenamic acid, and naproxen were in good agreemεnt with actual measured concentrations, which demonstrated the utility of PhATE1M as a predictive tool. 1n conclusion, PhATE1M, although it does not intend to accurately represent reality, could be utilizεd for rapid prε, dictions of the environmental concentrations of pharmaceuticals.

A Study on Distribution System of Pharmaceuticals in the Korea

김판진,류충열,남궁석,전타식,윤명길 한국유통과학회 2008 유통과학연구 Vol.6 No.2

This study examined state of local pharmaceuticals industry and investigated distribution system. The study found out associated problems as well as improvements of distribution system of local pharmaceuticals. Finally, to improve distribution system of local pharmaceuticals, the study investigated distribution system of 10 kinds of pharmaceuticals of ‘J' Company being a leading local manufacturer of local pharmaceuticals, and found out improvements of the distribution system. The study collected and compiled ‘J' Company's internal slips and reporting material from April 1, 2008 to July 31, 2008, and interviewed persons in charge continuously to find out state and problems of the distribution system.

간호대학생의 환경행동 지식과 태도가 불용의약품에 관한 환경행동 수행의도에 미치는 영향

김경자(Kim Kyoung Ja),김현지(Kim Hyun Ji) 학습자중심교과교육학회 2020 학습자중심교과교육연구 Vol.20 No.8

본 연구에서는 간호대학생의 환경행동 지식과 태도 가 불용의약품에 관한 환경행동 수행의도에 미치는 영향을 파악함으로서, 간호대학생의 환경 및 간호역량 교육구성에 필요한 기초자료를 제공하기 위하여 계획하였다. 연구대상은 간호대학생으로 투약 및 환경간호에 대한 기본적인 교육을 받은 3, 4학년 학생이며, 구조화 된 설문지를 사용하여 2018년 6월 1일부터 8월 30일까지 자료를 수집하였다. 자료처리는 SPSS 20.0 프로그램을 활용하여 분석하였다. 연구결과 불용의약품 관련 환경행동 수행의도는 환경행동 실천(r=.388, p<.001), 환경태도(r=.252, p=.002), 환경인식(r=.206, p=.012)과 양의 상관관계를 나타내었다. 환경인식, 태도, 행동이 불용의약품 처리 의도에 영향을 미치는 정도를 파악한 결과, 환경인식(β=.26, p=.005), 환경 행동(β=.19, p=.037)이 주 영향요인으로 나타났고 이에 대한 설명력은 17.1%였다. 본 연구결과를 통하여 간호대학생의 불용의약품에 대한 수행의도를 파악할 수 있었고, 영향요인으로는 환경 인식과 환경행동임을 확인하였다. 이를 향상시키기 위해 간호대학생의 환경교과 및 간호역량 교육구성에 필요한 기초자료를 제공할 것으로 기대된다. The purpose of this study was to investigate the influential factors on environmental behavior intention regarding unused pharmaceuticals. A cross-sectional design was used, in which a structured questionnaire was administered to 145 3rd and 4th grade nursing students who learned about basic knowledge regarding medication and healthy environment, from June 1st to August 30th, 2018. Data were analyzed using descriptive statistics, t-test or one way ANOVA, Pearson correlation coefficients, and multiple regression. Environmental behavior intention regarding unused pharmaceuticals was correlated with environmental behavior(r=.388, p<.001), environmental attitude(r=.252, p=002), environmental perception(r=.206, p=.012). The regression model explained approximately 17.1% of environmental behavior intention regarding unused pharmaceuticals. Meanwhile, environmental perception(β=.26, p=.005), and environmental behavior(β=.19, p=.037) were determined to be influencing factors on environmental behavior intention regarding unused pharmaceuticals. This study has significance as it suggested that environmental behavior intention regarding unused pharmaceuticals is affected by environmental perception and behavior. Therefore, to enhance the environmental behavior intention regarding unused pharmaceuticals, environmental education for nursing students that can be applied in nursing curriculum should be develop.

Several Human Pharmaceutical Residues in Aquatic Environment may result in Endocrine Disruption in Japanese Medaka (Oryzias latipes)

Hee Joo Kang,Hyun Soo Kim,Kyung Ho Choi,Kyung Tae Kim,Pan Gyi Kim 한국환경보건학회 2005 한국환경보건학회지 Vol.31 No.3

This study was designed to determine the estrogenic effect of the pharmaceuticals on several measures of endocrine function in adult fish (Oryzias latipes) that was induced by residual pharmaceuticals. 17-estradiol was used positive control that was induced vitellogenin (Vtg) in male fish. Some common pharmaceuticals were used caffeine, ketoconazole, acetaminophen and diltiazem. Vtg was qualified and quantified through Western blot and ELISA. Following SDS gel electrophoresis, the dominant protein band was identified to molecular weight approximately 205 kDa in whole body samples of vitellogenic female. As a exposed 17-estradiol, female fish didn't showed significant difference, but 3-5 days exposure of 17-estradiol to male fish induced 63.07‰ of total protein, the value was elevated than control male fish (0.76‰) and was showed a large significant difference p<0.01. In case of general pharmaceuticals, female fish didn’t showed significant difference, while male fish did showed significant difference. Vtg was induced significantly at male fish over caffeine 2 ppm. Same as ketoconazole 10 ppm, acetaminophen 4 ppm, diltiazem 1pm induced vtg significantly at male fish. This study confirmed Vtg by whole body samples of pharmaceutical compounds even at low concentration (ppm). In addition, the result of each chemical tested in sequence of concentration range, each chemical was increased Vtg concentration in fish when increased exposure range of each. Therefore, if residual pharmaceutic chemucals increase in aquatic environment, that will be a serious problem at fish, human and ecosystem.

Plant-made pharmaceuticals: exploring studies for the production of recombinant protein in plants and assessing challenges ahead

이주호,이선경,박종숙,이경렬 한국식물생명공학회 2023 Plant biotechnology reports Vol.17 No.1

The production of pharmaceutical compounds in plants is attracting increasing attention, as plant-based systems can be less expensive, safer, and more scalable than mammalian, yeast, bacterial, and insect cell expression systems. Here, we review the history and current status of plant-made pharmaceuticals. Producing pharmaceuticals in plants requires pairing the appropriate plant species with suitable transformation technology. Pharmaceuticals have been produced in tobacco, cereals, legumes, fruits, and vegetables via nuclear transformation, chloroplast transformation, transient expression, and transformation of suspension cell cultures. Despite this wide range of species and methods used, most such efforts have involved the nuclear transformation of tobacco. Tobacco readily generates large amounts of biomass, easily accepts foreign genes, and is amenable to stable gene expression via nuclear transformation. Although vaccines, antibodies, and therapeutic proteins have been produced in plants, such pharmaceuticals are not readily utilized by humans due to differences in glycosylation, and few such compounds have been approved due to a lack of clinical data. In addition, achieving an adequate immune response using plant-made pharmaceuticals can be difficult due to low rates of production compared to other expression systems. Various technologies have recently been developed to help overcome these limitations; however, plant systems are expected to increasingly become widely used expression systems for recombinant protein production.