Abstract：In this paper, the degradation of two target pharmaceuticals, carbamazepine (CBZ) and diclofenac (DCF), via dissimilatory Mn(IV) reduction was investigated in an anaerobic biological filter filling with manganese ores. The sediment from Jialing River was used as inoculum of the filter. Effects of extra organic carbon (sodium acetate) and adding extra MnO2 on degradation were also studied. The results indicated that the anaerobic biofilter column could achieve 25.23% and 32.44% removal of CBZ and DCF from 10μg/L, respectively, with no extra sodium acetate or MnO2 added. The contribution of dissimilatory Mn(IV) reduction to total CBZ removal was only 2.81% while that to DFC was 14.87%. Adding 0.5g/L of sodium acetate or 25g of MnO2 could improve the removal efficiency of CBZ by 6.35% and 4.63%, respectively, through dissimilatory Mn(IV) reduction, while no significant effect on the DCF removal was observed. This study could provide a new idea for the degradation of resistant organic pharmaceuticals.
翟俊, 胡炜, 王泉峰, 尹雪娇, 陈妮. 异化Mn(IV)还原耦合降解卡马西平及双氯芬酸[J]. 中国环境科学, 2021, 41(4): 1704-1710.
ZHAI Jun, HU Wei, WANG Quan-feng, YIN Xue-jiao, CHEN Ni. Degradation of carbamazepine and diclofenac via dissimilatory Mn(IV) reduction. CHINA ENVIRONMENTAL SCIENCECE, 2021, 41(4): 1704-1710.
Li Z, Zlabek V, Velisek J, et al. Acute toxicity of carbamazepine to juvenile rainbow trout (Oncorhynchus mykiss):Effects on antioxidant responses, hematological parameters and hepatic Erod[J]. Ecotoxicology and Environmental Safety, 2011,74(3):319-327.
[2]
Kawabata K, Sugihara K, Sanoh S, et al. Photodegradation of pharmaceuticals in the aquatic environment by sunlight and UV-A,-B and-C irradiation[J]. Journal of Toxicological Sciences, 2013,38(2):215-223.
[3]
Guiloski I C, Stein Piancini L D, Dagostim A C, et al. Effects of environmentally relevant concentrations of the anti-inflammatory drug diclofenac in freshwater fish Rhamdia quelen[J]. Ecotoxicology and Environmental Safety, 2017,139:291-300.
[4]
蒋科伟,刘敏敏,曾超.环境中的药物来源、归趋及环境影响分析[J]. 环境工程技术学报, 2015,5(6):539-544. Jiang K W, Liu M M, Zeng C. Analyses on Source, Fate and Environmental Impact of Pharmaceuticals in Environment[J]. Journal of Environmental Engineering Technology, 2015,5(6):539-544.
[5]
Ferrari B, Paxeus N, Lo Giudice R, et al. Ecotoxicological impact of pharmaceuticals found in treated wastewaters:study of carbamazepine, clofibric acid, and diclofenac[J]. Ecotoxicology and Environmental Safety, 2003,56(3):450.
[6]
孙继成,吴志超,王志伟,等.电化学耦合膜工艺去除饮用水中卡马西平[J]. 中国环境科学, 2018,(1):193-201. Sun J C, Wu Z C, Wang Z W, et al. The electrochemical coupled membrane process for the removal of CBZ in drinking water[J]. China Environmental Science, 2018,(1):193-201.
[7]
Vieno N, Sillanpää M. Fate of diclofenac in municipal wastewater treatment plant-a review[J]. Environment International, 2014,69(30):28-39.
[8]
夏文君,徐劼,刘锋,等.秸秆生物炭对双氯芬酸钠的吸附性能研究[J]. 中国环境科学, 2019,39(3):160-166. Xia W J, Xu J, Liu F, et al. Adsorption of diclofenac on straw-biochar[J]. China Environmental Science, 2019,39(3):160-166.
[9]
Lonappan L, Brar S K, Das R K, et al. Diclofenac and its transformation products:Environmental occurrence and toxicity-A review[J]. Environment International, 2016,96:127-138.
[10]
Zhang Y, Geissen S, Gal C. Carbamazepine and diclofenac:Removal in wastewater treatment plants and occurrence in water bodies[J]. Chemosphere, 2008,73(8):1151-1161.
[11]
Ternes, T.A., Occurrence of drugs in German sewage treatment plants and rivers[J]. Water Research, 1998,32(11):3245-3260.
[12]
Benoǐt F, Mons R, Vollat B, et al. Environmental risk assessment of six human pharmaceuticals:Are the current environmental risk assessment procedures sufficient for the protection of the aquatic environment[J]. Environmental Toxicology and Chemistry, 2004, 23(5):1344.
[13]
Wang J, Wang S. Removal of pharmaceuticals and personal care products (PPCPs) from wastewater:A review[J]. Journal of Environmental Management, 2016,182:620-640.
[14]
Liu W, Sutton N B, Rijnaarts H H M, et al. Anaerobic biodegradation of pharmaceutical compounds coupled to dissimilatory manganese (IV) or iron (Ⅲ) reduction[J]. Journal of Hazardous Materials, 2018. DOI:10.1016/j.jhazmat.2018.04.078.
[15]
Alette L, Nadia I, Teun V, et al. Microbial Removal of the Pharmaceutical Compounds Ibuprofen and Diclofenac from Wastewater[J]. Biomed Research International, 2013,2013:1-9.
[16]
Zhai J, Wang Q, Li Q, et al. Degradation mechanisms of carbamazepine by δ-MnO2:Role of protonation of degradation intermediates[J]. Science of The Total Environment, 2018,640-641:981-988.
[17]
Ye Y, Feng Y, Bruning H, et al. Photocatalytic degradation of metoprolol by TiO2nanotube arrays and UV-LED:Effects of catalyst properties, operational parameters, commonly present water constituents, and photo-induced reactive species[J]. Applied Catalysis B-environmental, 2018,220:171-181.
[18]
Lovley D. Dissimilatory Fe(Ⅲ)-and Mn(IV)-Reducing Prokaryotes[M]. Prokaryotes, 2006:635-658.
[19]
《水和废水监测分析方法》[M]. 北京:中国环境科学出版社, 2002:370-372. Water and Wastewater Monitoring and Analysis Methods[M]. Beijing:China Environmental Science Press, 2002:370-372.
[20]
Dolores C M O, Julia M, Juan Luis S, et al. An affordable method for the simultaneous determination of the most studied pharmaceutical compounds as wastewater and surface water pollutants[J]. Journal of Separation Science, 2015,32(18):3064-3073.
[21]
周康.食品微生物生长预测模型研究新进展[J]. 微生物学通报, 2008,35(4):589-594. Zhou K. New Advances in Predictive Food Microbial Growth Model[J]. Microbiology China, 2008,35(4):589-594.
[22]
易维洁,曲东,黄婉玉,等.淹水培养时间对水稻土中Fe(Ⅲ)异化还原能力的影响[J]. 农业环境科学学报, 2010,29(9):1723-1729. Yi W J, Qu D, Huang W Y, et al. Effect of Flooding Time on Dissimilatory Iron(Ⅲ) Reduction in Paddy Soil[J]. Journal of Agro-Environment Science, 2010,29(9):1723-1729.
[23]
金圣圣,张丽梅,贺纪正.锰氧化物与环境中有机物的作用及其在环境修复中的应用[J]. 环境科学学报, 2008,(12):2394-2403. Jin S S, Zhang L M, He J Z. Review of reactions of manganese oxides with organic compounds and applications of MnOx in environmental remediation[J]. Acta Scientiae Circumstantiae, 2008,(12):2394-2403.
[24]
廖汝娥,于志强,高娜,等.二氧化锰体系中环丙沙星的氧化转化研究[J]. 生态环境学报, 2011,20(Z1):1143-1146. Liao R E, Yu Z Q, Gao N, et al. Oxidative transformation of ciprofloxacin in the presence of manganese oxide[J]. Ecology and Environmental Sciences, 2011,20(Z1):1143-1146.
[25]
杨梦丽.厌氧锰矿反应柱对水环境中典型PPCPs的去除效果和机理研究[D]. 重庆:重庆大学, 2016. Yang M L. Research on typical PPCPs removal effect and mechanism by manganese ore columnar reactor in anaerobic condition[D]. Chongqing:Chongqing Universty, 2016.
[26]
肖君.锰矿石人工湿地甲烷消减及碳的归趋途径研究[D]. 重庆:重庆大学, 2017. X J. Study on the reduction of methane and carbon removal pathways in the constructed wetland of manganese ore[D]. Chongqing:Chongqing Universty, 2017.
[27]
Liu W, Langenhoff A A M, Sutton N B, et al. Application of manganese oxides under anoxic conditions to remove diclofenac from water[J]. Journal of Environmental Chemical Engineering, 2018,6(4):5061-5068.
[28]
Liu W, Sutton N B, Rijnaarts H H M, et al. Anoxic conditions are beneficial for abiotic diclofenac removal from water with manganese oxide (MnO2)[J]. Environmental Science and Pollution Research, 2018,25(10):10141-10147.
[29]
Remucal C K, Ginder-Vogel M. A critical review of the reactivity of manganese oxides with organic contaminants[J]. Environmental Science:Processes & Impacts, 2014,16(6):1247-1266.
[30]
Balgooyen S, Alaimo P J, Remucal C K, et al. Structural Transformation of MnO2during the Oxidation of Bisphenol A[J]. Environmental Science & Technology, 2017,51(11):6053-6062.
[31]
Forrez I, Carballa M, Verbeken K, et al. Diclofenac oxidation by biogenic manganese oxides[J]. Environmental Science & Technology, 2010,44(9):3449-3454.
[32]
Jin X, Wang F, Gu C, et al. The interactive biotic and abiotic processes of DDT transformation under dissimilatory iron-reducing conditions[J]. Chemosphere, 2015,138:18-24.
