华南与华北典型城市水环境抗生素分布特征与光催化降解研究

广泛使用抗生素治疗人类、动物和植物感染性疾病，导致水环境中抗生素污染严重，且对公众健康和水生生物构成潜在威胁。因此，抗生素污染问题在世界范围内受到高度关注。本研究旨在调查我国华南、华北两座重要城市的40种抗生素的污染特征，评估抗生素的水环境生态风险，并在此基础上开发高效降解环境浓度抗生素的光催化技术。华南、华北区域内的两座城市由于气候和经济发展水平不同，抗生素的污染种类、浓度和时空分布特点存在差异，通过对比两市抗生素分布特征，可以更加系统全面揭示不同地域条件下抗生素在不同环境介质中的迁移转化规律，为我国抗生素的污染防治提供数据与理论支撑。

针对华南地区某市夏季和冬季的地下水样品中40种抗生素的检出、季节分布和生态风险等展开研究。抗生素的总浓度范围分别为夏季34.73~1344.17 ng/L，冬季1.39~633.84 ng/L，夏季地下水抗生素污染浓度高于冬季。夏季降雨量增加，地表水地下水交换作用更强，水溶性较强更容易迁移的抗生素在地下水中含量增高，例如磺胺对甲氧嘧啶（检出率：40.32%）和磺胺甲恶唑（检出率：50%）在地下水中含量较高，浓度分别为~123.61 ng/L和~253.07 ng/L。研究表明磺胺甲基嘧啶、磺胺甲二唑、诺氟沙星、环丙沙星和达氟沙星等抗生素对抗性基因（Antibiotic Resistance Genes，ARGs）扩散有显著促进作用。此外，SO42-、F-、TDS、DO和pH等水质参数对ARGs扩散的促进作用也不容忽视。

华北地区某市水环境中地表水、地下水和沉积物中抗生素污染浓度范围分别为12.71~260.56 ng/L、~196.12 ng/L和38.03~406.31 ng/g。在地表水和沉积物中，头孢菌素类和喹诺酮类是主要检出抗生素，在地表水中分别占抗生素总浓度的45%和16%，在沉积物中分别占总抗生素浓度的62%和32%，这一结果表明两种介质之间存在重要的交互转化作用。在<50 m深度的浅层地下水中抗生素浓度最高（平均浓度为79.22±56.46 ng/L），表明地表水是地下水中抗生素污染的主要来源。阿莫西林和磺胺甲恶唑在地表水和地下水中的风险较高，应作为优先控制抗生素。此外，在华北某市的沉积物中发现了抗生素对ARGs的选择压力，因为sulA的富集与螺旋霉素和林可霉素显著相关，而blaOXA-1的富集与罗红霉素、环丙沙星、氧氟沙星和磺胺吡啶显著相关。

本研究采用光催化氧化法降解两城市均需优先控制的抗生素磺胺甲恶唑，选用廉价易得、无毒、稳定性高的市售二氧化钛（TiO2）作为催化剂，选用可产生多样化活性基团的强还原性含硫化合物连二亚硫酸钠（DTN，S2O42-）作为自由基产生源。研究结果表明使用TiO2作为催化剂活化DTN实现了磺胺甲恶唑的高效降解。在TiO2/DTN体系中，1 h内便可实现磺胺甲恶唑100%的高效去除。通过探究催化剂用量和DTN浓度对降解效率的影响，最终确定最优化反应条件TiO2投加量为5 mg，DTN与磺胺甲恶唑摩尔比为20:1。磺胺甲恶唑可以在碱性条件（pH为7.0~11.0）下被高效的去除，在酸性条件（pH为1.0~5.0）下受到显著的抑制。在碳酸氢根的存在下，磺胺甲恶唑的降解基本不受影响，浓度50~200 mg/L时有促进作用。但是在硝酸根，氯离子和腐殖酸的存在下，磺胺甲恶唑的降解则会受到显著的抑制，抑制作用随着浓度增加而增加。通过自由基淬灭和捕获实验，证明了主要活性基团为硫酸根自由基、羟基自由基和单线态氧。

[1] CHEN H, JING L, TENG Y, et al. Characterization of antibiotics in a large-scale river system of China: Occurrence pattern, spatiotemporal distribution and environmental risks[J]. Science of the Total Environment，2018，618：409-418.
[2] LU L, LIU J, LI Z, et al. Occurrence and distribution of tetracycline antibiotics and resistance genes in longshore sediments of the Three Gorges Reservoir, China[J]. Frontiers in Microbiology，2018，9：1911.
[3] HU Y, YAN X, SHEN Y, et al. Antibiotics in surface water and sediments from Hanjiang River, Central China: Occurrence, behavior and risk assessment[J]. Ecotoxicology and Environmental Safety，2018，157：150-158.
[4] BEN Y, FU C, HU M, et al. Human health risk assessment of antibiotic resistance associated with antibiotic residues in the environment: A review[J]. Environmental Research，2019，169：483-493.
[5] 刘昔，王智，王学雷，等. 我国典型区域地表水环境中抗生素污染现状及其生态风险评价[J]. 环境科学，2019，40（05）：2094-2100.
[6] 申立娜，张璐璐，秦珊，等. 白洋淀喹诺酮类抗生素与微生物群落结构和多样性相关性研究[J]. 环境科学学报，2020，40（02）：574-584.
[7] XU Z, LI T, BI J, et al. Spatiotemporal heterogeneity of antibiotic pollution and ecological risk assessment in Taihu Lake Basin, China[J]. Science of the Total Environment，2018，643：12-20.
[8] KRAUSE K M, SERIO A W, KANE T R, et al. Aminoglycosides: An overview[J]. Cold Spring Harbor Perspectives in Medicine，2016，6（6）：a27029.
[9] ZHAO C, WANG Z, WANG C, et al. Photocatalytic degradation of DOM in urban stormwater runoff with TiO2 nanoparticles under UV light irradiation: EEM-PARAFAC analysis and influence of co-existing inorganic ions[J]. Environmental Pollution，2018，243：177-188.
[10] MANZETTI S, GHISI R. The environmental release and fate of antibiotics[J]. Marine Pollution Bulletin，2014，79（1-2）：7-15.
[11] HU Y, CHENG H, TAO S. Environmental and human health challenges of industrial livestock and poultry farming in China and their mitigation[J]. Environment International，2017，107：111-130.
[12] MCDONNELL L, ARMSTRONG D, ASHWORTH M, et al. National disparities in the relationship between antimicrobial resistance and antimicrobial consumption in Europe: An observational study in 29 countries[J]. Journal of Antimicrobial Chemotherapy，2017，72（11）：3199-3204.
[13] TEUBER M. Veterinary use and antibiotic resistance[J]. Current Opinion in Microbiology，2001，4：493-499.
[14] BROWNE A J, CHIPETA M G, HAINES W G, et al. Global antibiotic consumption and usage in humans, 2000-2018: A spatial modelling study[J]. Lancet Planet Health，2021，5（12）：e893-e904.
[15] 田吉宸，曾颖，舒兴权，等. 水环境中抗生素污染现状及环境效应研究进展[J]. 广东化工，2021，48（16）：150-151.
[16] ZHANG Q, YING G, PAN C, et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China: Source analysis, multimedia modeling, and linkage to bacterial resistance[J]. Environmental Science & Technology，2015，49（11）：6772-6782.
[17] TSUTSUI A, YAHARA K, SHIBAYAMA K. Trends and patterns of national antimicrobial consumption in Japan from 2004 to 2016[J]. Journal of Infection and Chemotherapy，2018，24（6）：414-421.
[18] WEI X, ZHANG Z, WALLEY J D, et al. Effect of a training and educational intervention for physicians and caregivers on antibiotic prescribing for upper respiratory tract infections in children at primary care facilities in rural China: A cluster-randomised controlled trial[J]. Lancet Global Health，2017，5（12）：e1258-e1267.
[19] GONG Y, LI H, YANG H, et al. Evaluation of the quality of antibiotic prescribing in primary care: A multicenter longitudinal study from Shenzhen, China[J]. Frontiers in Pharmacology，2021，11：617260.
[20] 杜实之. 环境中抗生素的残留、健康风险与治理技术综述[J]. 环境科学与技术，2021，44（09）：37-48.
[21] LOW K, CHAI L, LEE C, et al. Prevalence and risk assessment of antibiotics in riverine estuarine waters of Larut and Sangga Besar River, Perak[J]. Journal of Oceanology and Limnology，2021，39（1）：122-134.
[22] NGIGI A N, MAGU M M, MUENDO B M. Occurrence of antibiotics residues in hospital wastewater, wastewater treatment plant, and in surface water in Nairobi County, Kenya[J]. Environmental Monitoring and Assessment，2020，192（1）：18.
[23] FERNANDES M J, PAÍGA P, SILVA A, et al. Antibiotics and antidepressants occurrence in surface waters and sediments collected in the north of Portugal[J]. Chemosphere，2020，239：124729.
[24] AZANU D, STYRISHAVE B, DARKO G, et al. Occurrence and risk assessment of antibiotics in water and lettuce in Ghana[J]. Science of the Total Environment，2018，622-623：293-305.
[25] HERNÁNDEZ F, CALıSTO-ULLOA N, GÓMEZ-FUENTES C, et al. Occurrence of antibiotics and bacterial resistance in wastewater and sea water from the Antarctic[J]. Journal of Hazardous Materials，2019，363：447-456.
[26] KAFAEI R, PAPARI F, SEYEDABADI M, et al. Occurrence, distribution, and potential sources of antibiotics pollution in the water-sediment of the northern coastline of the Persian Gulf, Iran[J]. Science of the Total Environment，2018，627：703-712.
[27] LIU X, ZHANG G, LIU Y, et al. Occurrence and fate of antibiotics and antibiotic resistance genes in typical urban water of Beijing, China[J]. Environmental Pollution，2019，246：163-173.
[28] LIU X, LIU Y, LU S, et al. Occurrence of typical antibiotics and source analysis based on PCA-MLR model in the East Dongting Lake, China[J]. Ecotoxicology and Environmental Safety，2018，163：145-152.
[29] 丁剑楠，刘舒娇，邹杰明，等. 太湖表层水体典型抗生素时空分布和生态风险评价[J]. 环境科学，2021，42（04）：1811-1819.
[30] CHENG J, JIANG L, SUN T, et al. Occurrence, seasonal variation and risk assessment of antibiotics in the surface water of North China[J]. Archives of Environmental Contamination and Toxicology，2019，77（1）：88-97.
[31] ZHANG P, ZHOU H, LI K, et al. Occurrence of pharmaceuticals and personal care products, and their associated environmental risks in a large shallow lake in North China[J]. Environmental Geochemistry and Health，2018，40（4）：1525-1539.
[32] LI S, SHI W, LI H, et al. Antibiotics in water and sediments of rivers and coastal area of Zhuhai City, Pearl River Estuary, South China[J]. Science of the Total Environment，2018，636：1009-1019.
[33] MEI X, SUI Q, LYU S, et al. Pharmaceuticals and personal care products in the urban river across the megacity Shanghai: Occurrence, source apportionment and a snapshot of influence of rainfall[J]. Journal of Hazardous Materials，2018，359：429-436.
[34] QIU W, SUN J, FANG M, et al. Occurrence of antibiotics in the main rivers of Shenzhen, China: Association with antibiotic resistance genes and microbial community[J]. Science of the Total Environment，2019，653：334-341.
[35] 李玉琼，童蕾，严涵，等. 河水-地下水交互带沉积物中抗生素和代谢产物提取方法优化及其分布特征[J]. 环境科学，2021，42（11）：5294-5302.
[36] 陈桂淋，武广元，苏帆，等. 我国地下水抗生素污染及生态风险研究进展[J]. 地下水，2020，42（05）：8-13.
[37] YAO L, WANG Y, TONG L, et al. Occurrence and risk assessment of antibiotics in surface water and groundwater from different depths of aquifers: A case study at Jianghan Plain, Estuary[J]. Ecotoxicology and Environmental Safety，2017，135：236-242.
[38] KIVITS T, BROERS H P, BEELTJE H, et al. Presence and fate of veterinary antibiotics in age-dated groundwater in areas with intensive livestock farming[J]. Environmental Pollution，2018，241：988-998.
[39] LI X, LIU C, CHEN Y, et al. Antibiotic residues in liquid manure from swine feedlot and their effects on nearby groundwater in regions of North China[J]. Environmental Science and Pollution Research，2018，25（12）：11565-11575.
[40] ZAINAB S M, JUNAID M, XU N, et al. Antibiotics and antibiotic resistant genes (ARGs) in groundwater: A global review on dissemination, sources, interactions, environmental and human health risks[J]. Water Research，2020，187：116455.
[41] CHEN Q, LI H, ZHOU X, et al. An underappreciated hotspot of antibiotic resistance: The groundwater near the municipal solid waste landfill[J]. Science of the Total Environment，2017，609：966-973.
[42] LI F, WEN D, BAO Y, et al. Insights into the distribution, partitioning and influencing factors of antibiotics concentration and ecological risk in typical bays of the East China Sea[J]. Chemosphere，2022，288：132566.
[43] CHEN L, LI H, LIU Y, et al. Distribution, residue level, sources, and phase partition of antibiotics in surface sediments from the inland river: A case study of the Xiangjiang River, south-central China[J]. Environmental Science and Pollution Research，2020，27（2）：2273-2286.
[44] WANG L, LI H, DANG J, et al. Occurrence, distribution, and partitioning of antibiotics in surface water and sediment in a typical tributary of Yellow River, China[J]. Environmental Science and Pollution Research，2021，28（22）：28207-28221.
[45] YANG J, YING G, ZHAO J, et al. Simultaneous determination of four classes of antibiotics in sediments of the Pearl Rivers using RRLC-MS/MS[J]. Science of the Total Environment，2010，408（16）：3424-3432.
[46] XU J, ZHANG Y, ZHOU C, et al. Distribution, sources and composition of antibiotics in sediment, overlying water and pore water from Taihu Lake, China[J]. Science of the Total Environment，2014，497：267-273.
[47] 解旭东，侯智昊，李楠，等. 中国胡焕庸线下方四区域沉积物和土壤中抗生素污染特征及生态风险评价[J]. 生态环境学报，2021，30（05）：1023-1033.
[48] LI Q, GAO J, ZHANG Q, et al. Distribution and risk assessment of antibiotics in a typical river in North China Plain[J]. Bulletin of Environmental Contamination and Toxicology，2017，98（4）：478-483.
[49] HARROWER J, MCNAUGHTAN M, HUNTER C, et al. Chemical fate and partitioning behavior of antibiotics in the aquatic environment: A review[J]. Environmental Toxicology and Chemistry，2021，40（12）：3275-3298.
[50] CHEN K, ZHOU J L. Occurrence and behavior of antibiotics in water and sediments from the Huangpu River, Shanghai, China[J]. Chemosphere，2014，95：604-612.
[51] LIANG X, CHEN B, NIE X, et al. The distribution and partitioning of common antibiotics in water and sediment of the Pearl River Estuary, South China[J]. Chemosphere，2013，92（11）：1410-1416.
[52] WUNDER D B, BOSSCHER V A, COK R C, et al. Sorption of antibiotics to biofilm[J]. Water Research，2011，45（6）：2270-2280.
[53] ZHANG L, SHEN L, QIN S, et al. Quinolones antibiotics in the Baiyangdian Lake, China: Occurrence, distribution, predicted no-effect concentrations (PNECs) and ecological risks by three methods[J]. Environmental Pollution，2020，256：113458.
[54] CHEN S, ZHANG W, LI J, et al. Ecotoxicological effects of sulfonamides and fluoroquinolones and their removal by a green alga (Chlorella vulgaris) and a cyanobacterium (Chrysosporum ovalisporum)[J]. Environmental Pollution，2020，263：114554.
[55] 廖洋，鲁金凤，曹轶群，等. 光催化降解对抗生素藻类毒性效应影响研究进展[J]. 环境化学，2021，40（1）：111-120.
[56] MAO Y, YU Y, MA Z, et al. Azithromycin induces dual effects on microalgae: Roles of photosynthetic damage and oxidative stress[J]. Ecotoxicology and Environmental Safety，2021，222：112496.
[57] YISA A G, CHIA M A, SHA ABA R I, et al. The antibiotic ciprofloxacin alters the growth, biochemical composition, and antioxidant response of toxin-producing and non-toxin-producing strains of Microcystis[J]. Journal of Applied Phycology，2021，33（4）：2145-2155.
[58] ZHENG Y, WANG Y, ZHENG M, et al. Exposed to sulfamethoxazole induced hepatic lipid metabolism disorder and intestinal microbiota changes on zebrafish (Danio rerio)[J]. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology，2022，253：109245.
[59] ROSAS R J R, OROZCO H J M, ELIZALDE V G A, et al. Teratogenic effects induced by paracetamol, ciprofloxacin, and their mixture on Danio rerio embryos: Oxidative stress implications[J]. Science of the Total Environment，2022，806：150541.
[60] HAN Y, MA Y, CHEN B, et al. Hazard assessment of beta-lactams: Integrating in silico and QSTR approaches with in vivo zebrafish embryo toxicity testing[J]. Ecotoxicology and Environmental Safety，2022，229：113106.
[61] WANG M, ZHAO J, WU L, et al. Effects of 4-epianhydrotetracycline on oxidative stress in zebrafish (Danio rerio) embryos[J]. Science of the Total Environment，2021，796：149047.
[62] YANG L, WANG T, ZHOU Y, et al. Contamination, source and potential risks of pharmaceuticals and personal products (PPCPs) in Baiyangdian Basin, an intensive human intervention area, China[J]. Science of the Total Environment，2021，760：144080.
[63] ONAL U, AKALIN H. Coronavirus disease 2019 and antibiotic stewardship-antibiotic usage in adult patients: Is it necessary? When should it be concerned?[J]. Balkan Medical Journal，2021，38（3）：150-155.
[64] NAKAYAMA R, INOUE-TSUDA M, MATSUI H, et al. Classification of the metallo β-lactamase subtype produced by the carbapenem-resistant Pseudomonas aeruginosa isolates in Japan[J]. Journal of Infection and Chemotherapy，2022，28（2）：170-175.
[65] 孙文龙，肖旸，李阳，等. 分流制雨水管网沉积物中典型抗生素抗性基因污染特性[J]. 环境科学学报，2020，40（11）：4018-4026.
[66] 冯雪梅，卫新来，陈俊，等. 高级氧化技术在废水处理中的应用进展[J]. 应用化工，2020，4（49）：993-996.
[67] ANIPSITAKIS G P, DIONYSIOU D D. Radical generation by the interaction of transition metals with common oxidants[J]. Environmental Science & Technology，2004，38（13）：3705-3712.
[68] 解永磊. UASB-A/O-Fenton组合工艺处理四环素类抗生素废水试验研究[D]. 天津：天津理工大学，2015：100.
[69] DODD M C, KOHLER H E, von GUNTEN U. Oxidation of antibacterial compounds by ozone and hydroxyl radical: Elimination of biological activity during aqueous ozonation processes[J]. Environmental Science & Technology，2009，43（7）：2498-2504.
[70] 王伟. 臭氧催化氧化降解水体中头孢噻肟钠的研究[D]. 秦皇岛：燕山大学，2019：35.
[71] 何锦垚，魏健，张嘉雯，等. 臭氧催化氧化-BAF组合工艺深度处理抗生素制药废水[J]. 环境工程学报，2019，13（10）：2385-2392.
[72] 王超，姚淑美，彭叶平，等. 高级氧化法处理抗生素废水研究进展[J]. 化工环保，2018，38（02）：135-140.
[73] WANG Y, SHEN C, ZHANG M, et al. The electrochemical degradation of ciprofloxacin using a SnO2-Sb/Ti anode: Influencing factors, reaction pathways and energy demand[J]. Chemical Engineering Journal，2016，296：79-89.
[74] NUNEZ GARCIA A, BOPARAI H K, O CARROLL D M. Enhanced dechlorination of 1,2-dichloroethane by coupled nano iron-dithionite treatment[J]. Environmental Science & Technology，2016，50（10）：5243-5251.
[75] OLEA M A U, BUENO J D J P, PÉREZ A X M. Nanometric and surface properties of semiconductors correlated to photocatalysis and photoelectrocatalysis applied to organic pollutants: A review[J]. Journal of Environmental Chemical Engineering，2021，9（6）：106480.
[76] LI J, WU N. Semiconductor-based photocatalysts and photoelectrochemical cells for solar fuel generation: A review[J]. Catalysis Science & Technology，2015，5（3）：1337-1972.
[77] 王建强，黄菊梅，马玉龙，等. 改性二氧化钛光催化技术在水污染治理中的研究进展[J]. 现代盐化工，2021，48（06）：9-11.
[78] WANG H, GAO Q, LI H, et al. One-pot synthesis of a novel hierarchical Co(II)-doped TiO2 nanostructure: Toward highly active and durable catalyst of peroxymonosulfate activation for degradation of antibiotics and other organic pollutants[J]. Chemical Engineering Journal，2019，368：377-389.
[79] VIGNESH K, RAJARAJAN M, SUGANTHI A. Photocatalytic degradation of erythromycin under visible light by zinc phthalocyanine-modified titania nanoparticles[J]. Materials Science in Semiconductor Processing，2014，23：98-103.
[80] LAN N T, ANH V H, AN H D, et al. Synthesis of C-N-S-tridoped TiO2 from Vietnam ilmenite ore and its visible light-driven-photocatalytic activity for tetracyline degradation[J]. Journal of Nanomaterials，2020，2020：1-14.
[81] BELTRÁN F J, AGUINACO A, GARCÍA-ARAYA J F, et al. Ozone and photocatalytic processes to remove the antibiotic sulfamethoxazole from water[J]. Water Research，2008，42（14）：3799-3808.
[82] ABELLÁN M N, BAYARRI B, GIMÉNEZ J, et al. Photocatalytic degradation of sulfamethoxazole in aqueous suspension of TiO2[J]. Applied Catalysis B: Environmental，2007，74（3-4）：233-241.
[83] HU L, FLANDERS P M, MILLER P L, et al. Oxidation of sulfamethoxazole and related antimicrobial agents by TiO2 photocatalysis[J]. Water Research，2007，41（12）：2612-2626.
[84] ZHANG W, BIAN Z, XIN X, et al. Comparison of visible light driven H2O2 and peroxymonosulfate degradation of norfloxacin using Co/g-C3N4[J]. Chemosphere，2021，262：127955.
[85] ZAMMOURI L, ABOULAICH A, CAPOEN B, et al. Enhancement under UV-visible and visible light of the ZnO photocatalytic activity for the antibiotic removal from aqueous media using Ce-doped Lu3Al5O12 nanoparticles[J]. Materials Research Bulletin，2018，106：162-169.
[86] HE S, ZHAI C, FUJITSUKA M, et al. Femtosecond time-resolved diffuse reflectance study on facet engineered charge-carrier dynamics in Ag3PO4 for antibiotics photodegradation[J]. Applied Catalysis B: Environmental，2021，281：119479.
[87] MAO W, ZHANG L, LIU Y, et al. Facile assembled N, S-codoped corn straw biochar loaded Bi2WO6 with the enhanced electron-rich feature for the efficient photocatalytic removal of ciprofloxacin and Cr(VI)[J]. Chemosphere，2021，263：127988.
[88] DURÁN-ÁLVAREZ J C, AVELLA E, RAMÍREZ-ZAMORA R M, et al. Photocatalytic degradation of ciprofloxacin using mono- (Au, Ag and Cu) and bi- (Au-Ag and Au-Cu) metallic nanoparticles supported on TiO2 under UV-C and simulated sunlight[J]. Catalysis Today，2016，266：175-187.
[89] CHANKHANITTHA T, NANAN S. Visible-light-driven photocatalytic degradation of ofloxacin (OFL) antibiotic and rhodamine B (RhB) dye by solvothermally grown ZnO/Bi2MoO6 heterojunction[J]. Journal of Colloid and Interface Science，2021，582：412-427.
[90] ZHANG D, QI J, JI H, et al. Photocatalytic degradation of ofloxacin by perovskite-type NaNbO3 nanorods modified g-C3N4 heterojunction under simulated solar light: Theoretical calculation, ofloxacin degradation pathways and toxicity evolution[J]. Chemical Engineering Journal，2020，400：125918.
[91] KULKARNI R M, MALLADI R S, HANAGADAKAR M S, et al. Ag-TiO2 nanoparticles for photocatalytic degradation of lomefloxacin[J]. Desalination and Water Treatment，2015（9）：1-8.
[92] CHEN Y, ZHANG X, WANG L, et al. Rapid removal of phenol/antibiotics in water by Fe-(8-hydroxyquinoline-7-carboxylic)/TiO2 flower composite: Adsorption combined with photocatalysis[J]. Chemical Engineering Journal，2020，402：126260.
[93] LI Q, JIA R, SHAO J, et al. Photocatalytic degradation of amoxicillin via TiO2 nanoparticle coupling with a novel submerged porous ceramic membrane reactor[J]. Journal of Cleaner Production，2019，209：755-761.
[94] VIGNESH K, RAJARAJAN M, SUGANTHI A. Photocatalytic degradation of erythromycin under visible light by zinc phthalocyanine-modified titania nanoparticles[J]. Materials Science in Semiconductor Processing，2014，23：98-103.
[95] MEHRDOOST A, YENGEJEH R J, MOHAMMADI M K, et al. Adsorption removal and photocatalytic degradation of azithromycin from aqueous solution using PAC/Fe/Ag/Zn nanocomposite[J]. Environmental Science and Pollution Research，2022，29（22）：33514-33527.
[96] KUMAR A, RANA A, GUO C, et al. Acceleration of photo-reduction and oxidation capabilities of Bi4O5I2/SPION@calcium alginate by metallic Ag: Wide spectral removal of nitrate and azithromycin[J]. Chemical Engineering Journal，2021，423：130173.
[97] DONG W, XIE W, SU X, et al. Review: Micro-organic contaminants in groundwater in China[J]. Hydrogeology Journal，2018，26（5）：1351-1369.
[98] 王娅南，黄合田，彭洁，等. 贵州草海喀斯特高原湿地水环境中典型抗生素的分布特征[J]. 环境化学，2020，39（04）：975-986.
[99] 包樱钰，李菲菲，温东辉. 我国海水养殖业的抗生素污染现状[J]. 海洋环境科学，2021，40（02）：294-302.
[100]BEN Y, HU M, ZHANG X, et al. Efficient detection and assessment of human exposure to trace antibiotic residues in drinking water[J]. Water Research，2020，175：115699.
[101]YANG J, HUANG Y, CHEN Y, et al. Multi-phase distribution, spatiotemporal variation and risk assessment of antibiotics in a typical urban-rural watershed[J]. Ecotoxicology and Environmental Safety，2020，206：111156.
[102]LIU T, ZHANG A N, WANG J, et al. Integrated biogeography of planktonic and sedimentary bacterial communities in the Yangtze River[J]. Microbiome，2018，6（1）：s40168.
[103]ZHANG S, GU J, WANG C, et al. Characterization of antibiotics and antibiotic resistance genes on an ecological farm system[J]. Journal of Chemistry，2015，2015：1-8.
[104]YUAN Q, ZHAI Y, MAO B, et al. Antibiotic resistance genes and intI1 prevalence in a swine wastewater treatment plant and correlation with metal resistance, bacterial community and wastewater parameters[J]. Ecotoxicology and Environmental Safety，2018，161：251-259.
[105]鲁金凤，王斌，廖洋，等. 水环境中残留抗生素的消毒副产物问题最新研究进展[J]. 中国给水排水，2020，36（04）：6-12.
[106]ZHANG B, QIN S, GUAN X, et al. Distribution of antibiotic resistance genes in karst river and its ecological risk[J]. Water Research，2021，203：117507.
[107]YANG C, LI Y, ZUO L, et al. Genomic epidemiology and antimicrobial susceptibility profile of enterotoxigenic Escherichia Coli from outpatients with diarrhea in Shenzhen, China, 2015-2020[J]. Frontiers in Microbiology，2021，12：732068.
[108]LI Y, LI Y, XIU L, et al. Typing of Neisseria gonorrhoeae isolates in Shenzhen, China from 2014-2018 reveals the shift of genotypes associated with antimicrobial resistance[J]. Antimicrobial Agents and Chemotherapy，2021，65（5）：e02311.
[109]GAO F, ZOU H, WU D, et al. Swine farming elevated the proliferation of acinetobacter with the prevalence of antibiotic resistance genes in the groundwater[J]. Environment International，2020，136：105484.
[110]ZAINAB S M, JUNAID M, XU N, et al. Antibiotics and antibiotic resistant genes (ARGs) in groundwater: A global review on dissemination, sources, interactions, environmental and human health risks[J]. Water Research，2020，187：116455.
[111]陈慧，剧泽佳，赵鑫宇，等. 石家庄地下水中喹诺酮类抗生素生态风险及其与环境因子的相关性[J]. 环境科学，2022，3：1-15.
[112]BARTELT H S, SNOW D D, DAMON P T, et al. Occurrence of steroid hormones and antibiotics in shallow groundwater impacted by livestock waste control facilities[J]. Journal of Contaminant Hydrology，2011，123（3-4）：94-103.
[113]STUART M, LAPWORTH D, CRANE E, et al. Review of risk from potential emerging contaminants in UK groundwater[J]. Science of the Total Environment，2012，416：1-21.
[114]LÓPEZ-SERNA R, JURADO A, VÁZQUEZ-SUÑÉ E, et al. Occurrence of 95 pharmaceuticals and transformation products in urban groundwaters underlying the metropolis of Barcelona, Spain[J]. Environmental Pollution，2013，174：305-315.
[115]CHARUAUD L, JARDÉ E, JAFFRÉZIC A, et al. Veterinary pharmaceutical residues in water resources and tap water in an intensive husbandry area in France[J]. Science of the Total Environment，2019，664：605-615.
[116]FICK J, SODERSTROM H, LINDBERG R H, et al. Pharmaceuticals and personal care products in the environment[J]. Environmental Toxicology and Chemistry，2009，28（12）：2522-2527.
[117]SZEKERES E, CHIRIAC C M, BARICZ A, et al. Investigating antibiotics, antibiotic resistance genes, and microbial contaminants in groundwater in relation to the proximity of urban areas[J]. Environmental Pollution，2018，236：734-744.
[118]姬建堂. 吉林某药厂地下水中有机污染物盐酸四环素的治理研究[D]. 大连：辽宁师范大学，2019：80.
[119]LIN Y, LAI W W, TUNG H, et al. Occurrence of pharmaceuticals, hormones, and perfluorinated compounds in groundwater in Taiwan[J]. Environmental Monitoring and Assessment，2015，187（5）：256.
[120]SZEKERES E, CHIRIAC C M, BARICZ A, et al. Investigating antibiotics, antibiotic resistance genes, and microbial contaminants in groundwater in relation to the proximity of urban areas[J]. Environmental Pollution，2018，236：734-744.
[121]MORASCH B. Occurrence and dynamics of micropollutants in a karst aquifer[J]. Environmental Pollution，2013，173：133-137.
[122]CABEZA Y, CANDELA L, RONEN D, et al. Monitoring the occurrence of emerging contaminants in treated wastewater and groundwater between 2008 and 2010. The Baix Llobregat (Barcelona, Spain)[J]. Journal of Hazardous Materials，2012，239-240：32-39.
[123]MCEACHRAN A D, SHEA D, BODNAR W, et al. Pharmaceutical occurrence in groundwater and surface waters in forests land-applied with municipal wastewater[J]. Environmental Toxicology and Chemistry，2016，35（4）：898-905.
[124]LOOS R, LOCORO G, COMERO S, et al. Pan-European survey on the occurrence of selected polar organic persistent pollutants in ground water[J]. Water Research，2010，44（14）：4115-4126.
[125]ZAINAB S M, JUNAID M, REHMAN M Y A, et al. First insight into the occurrence, spatial distribution, sources, and risks assessment of antibiotics in groundwater from major urban-rural settings of Pakistan[J]. Science of the Total Environment，2021，791：148298.
[126]徐建，胡鹏，吕佳佩，等. 水环境中抗生素和抗性基因污染特征及控制措施[J]. 科技导报，2018，36（15）：13-23.
[127]VIKESLAND P, GARNER E, GUPTA S, et al. Differential drivers of antimicrobial resistance across the world[J]. Accounts of Chemical Research，2019，52（4）：916-924.
[128]JANG J, KIM M, BAEK S, et al. Hydrometeorological influence on antibiotic-resistance genes (ARGs) and bacterial community at a recreational beach in Korea[J]. Journal of Hazardous Materials，2021，403：123599.
[129]HONDA R, TACHI C, YASUDA K, et al. Estimated discharge of antibiotic-resistant bacteria from combined sewer overflows of urban sewage system[J]. NPJ Clean Water，2020，3（1）：15.
[130]SHEN S, YANG S, ZHANG D, et al. Spatial distribution of antibiotic resistance genes of the Zaohe-Weihe Rivers, China: Exerting a bottleneck in the hyporheic zone[J]. Environmental Science and Pollution Research，2022，29（25）：38410-38424.
[131]ZHANG H, WANG Y, LIU P, et al. Unveiling the occurrence, hosts and mobility potential of antibiotic resistance genes in the deep ocean[J]. Science of the Total Environment，2022，816：151539.
[132]HENRIQUES I, TACÃO M, LEITE L, et al. Co-selection of antibiotic and metal(loid) resistance in gram-negative epiphytic bacteria from contaminated salt marshes[J]. Marine Pollution Bulletin，2016，109（1）：427-434.
[133]苗荪，陈磊，左剑恶. 环境中抗生素抗性基因丰度与抗生素和重金属含量的相关性分析：基于Web of Science数据库检索[J]. 环境科学，2021，42（10）：4925-4932.
[134]HUANG Y, LIU Y, DU P, et al. Occurrence and distribution of antibiotics and antibiotic resistant genes in water and sediments of urban rivers with black-odor water in Guangzhou, South China[J]. Science of the Total Environment，2019，670：170-180.
[135]WANG Z, HAN M, LI E, et al. Distribution of antibiotic resistance genes in an agriculturally disturbed lake in China: Their links with microbial communities, antibiotics, and water quality[J]. Journal of Hazardous Materials，2020，393：122426.
[136]CHENG D, LIU X, WANG L, et al. Seasonal variation and sediment-water exchange of antibiotics in a shallower large lake in North China[J]. Science of the Total Environment，2014，476-477：266-275.
[137]CHEN K, ZHOU J L. Occurrence and behavior of antibiotics in water and sediments from the Huangpu River, Shanghai, China[J]. Chemosphere，2014，95：604-612.
[138]WANG W, WANG H, ZHANG W, et al. Occurrence, distribution, and risk assessment of antibiotics in the Songhua River in China[J]. Environmental Science and Pollution Research，2017，24（23）：19282-19292.
[139]ARSAND J B, HOFF R B, JANK L, et al. Presence of antibiotic resistance genes and its association with antibiotic occurrence in Dilúvio River in southern Brazil[J]. Science of the Total Environment，2020，738：139781.
[140]CHEN L, LANG H, LIU F, et al. Presence of antibiotics in shallow groundwater in the northern and southwestern regions of China[J]. Groundwater，2018，56（3）：451-457.
[141]ZUO R, LIU X, ZHANG Q, et al. Sulfonamide antibiotics in groundwater and their migration in the vadose zone: A case in a drinking water resource[J]. Ecological Engineering，2021，162：106175.
[142]MA Y, LI M, WU M, et al. Occurrences and regional distributions of 20 antibiotics in water bodies during groundwater recharge[J]. Science of the Total Environment，2015，518-519：498-506.
[143]SZEKERES E, CHIRIAC C M, BARICZ A, et al. Investigating antibiotics, antibiotic resistance genes, and microbial contaminants in groundwater in relation to the proximity of urban areas[J]. Environmental Pollution，2018，236：734-744.
[144]RADOVIĆ T, GRUJIĆ S, PETKOVIĆ A, et al. Determination of pharmaceuticals and pesticides in river sediments and corresponding surface and ground water in the Danube River and tributaries in Serbia[J]. Environmental Monitoring and Assessment，2015，187（1）：4092.
[145]CHARUAUD L, JARDÉ E, JAFFRÉZIC A, et al. Veterinary pharmaceutical residues in water resources and tap water in an intensive husbandry area in France[J]. Science of the Total Environment，2019，664：605-615.
[146]STUART M, LAPWORTH D, CRANE E, et al. Review of risk from potential emerging contaminants in UK groundwater[J]. Science of the Total Environment，2012，416：1-21.
[147]ELLIOTT S M, ERICKSON M L, KRALL A L, et al. Concentrations of pharmaceuticals and other micropollutants in groundwater downgradient from large on-site wastewater discharges[J]. Plos One，2018，13（11）：e206004.
[148]FRAM M S, BELITZ K. Occurrence and concentrations of pharmaceutical compounds in groundwater used for public drinking-water supply in California[J]. Science of the Total Environment，2011，409（18）：3409-3417.
[149]SU H, WANG W, JIA Y, et al. Impact of urbanization on precipitation and temperature over a lake-marsh wetland: A case study in Xiong’an New Area, China[J]. Agricultural Water Management，2021，243：106503.
[150]NIETO J J I, TORRES P R A, BOTERO C A M, et al. Pharmaceuticals and environmental risk assessment in municipal wastewater treatment plants and rivers from Peru[J]. Environment International，2021，155：106674.
[151]LIU J, LU J, TONG Y, et al. Occurrence and elimination of antibiotics in three sewage treatment plants with different treatment technologies in Urumqi and Shihezi, Xinjiang[J]. Water Science and Technology，2017，75（6）：1474-1484.
[152]NIU B, WANG N, CHEN Y, et al. Tourmaline synergized with persulfate for degradation of sulfadiazine: Influencing parameters and reaction mechanism[J]. Separation and Purification Technology，2021，257：117893.
[153]GHASEMI M, KHATAEE A, GHOLAMI P, et al. In-situ electro-generation and activation of hydrogen peroxide using a CuFeNLDH-CNTs modified graphite cathode for degradation of cefazolin[J]. Journal of Environmental Management，2020，267：110629.
[154]BAI Y, MENG W, XU J, et al. Occurrence, distribution and bioaccumulation of antibiotics in the Liao River Basin in China[J]. Environmental Science: Processes & Impacts，2014，16（3）：586.
[155]HU X, HE K, ZHOU Q. Occurrence, accumulation, attenuation and priority of typical antibiotics in sediments based on long-term field and modeling studies[J]. Journal of Hazardous Materials，2012，225-226：91-98.
[156]YANG J, YING G, ZHAO J, et al. Simultaneous determination of four classes of antibiotics in sediments of the Pearl Rivers using LC-MS[J]. Science of the Total Environment，2010，408（16）：3424-3432.
[157]LIU Y, FENG M, WANG B, et al. Distribution and potential risk assessment of antibiotic pollution in the main drinking water sources of Nanjing, China[J]. Environmental Science and Pollution Research，2020，27（17）：21429-21441.
[158]TANG X, CUI Z, BAI Y, et al. Indirect photodegradation of sulfathiazole and sulfamerazine: Influence of the CDOM components and seawater factors (salinity, pH, nitrate and bicarbonate)[J]. Science of the Total Environment，2021，750：141762.
[159]MANNIELLO M D, DEL GAUDIO P, PORTA A, et al. Aerodynamic properties, solubility and in vitro antibacterial efficacy of dry powders prepared by spray drying: Clarithromycin versus its hydrochloride salt[J]. European Journal of Pharmaceutics and Biopharmaceutics，2016，104：1-6.
[160]陈莹. 西安市地表水环境中典型抗生素污染特征及风险评估[D]. 西安：西安科技大学，2021：80.
[161]CI M, ZHANG G, YAN X, et al. Occurrence of antibiotics in the Xiaoqing River Basin and antibiotic source contribution: A case study of Jinan City, China[J]. Environmental Science and Pollution Research，2021，28（20）：25241-25254.
[162]VALDÉS M E, SANTOS L H M L, RODRÍGUEZ CASTRO M C, et al. Distribution of antibiotics in water, sediments and biofilm in an urban river (Córdoba, Argentina, LA)[J]. Environmental Pollution，2021，269：116133.
[163]NGUMBA E, GACHANJA A, NYIRENDA J, et al. Occurrence of antibiotics and antiretroviral drugs in source-separated urine, groundwater, surface water and wastewater in the peri-urban area of Chunga in Lusaka, Zambia[J]. Water S.A.，2020，46（2）：278-284.
[164]WU J, LIU J, PAN Z, et al. Spatiotemporal distributions and ecological risk assessment of pharmaceuticals and personal care products in groundwater in North China[J]. Hydrology Research ，2020，51（5）：911-924.
[165]TONG L, HUANG S, WANG Y, et al. Occurrence of antibiotics in the aquatic environment of Jianghan Plain, Central China[J]. Science of the Total Environment，2014，497-498：180-187.
[166]HUANG F, AN Z, MORAN M J, et al. Recognition of typical antibiotic residues in environmental media related to groundwater in China (2009-2019)[J]. Journal of Hazardous Materials，2020，399：122813.
[167]ZHOU J, BROODBANK N. Sediment-water interactions of pharmaceutical residues in the river environment[J]. Water Research，2014，48：61-70.
[168]ZHOU L, WU Q L, ZHANG B, et al. Occurrence, spatiotemporal distribution, mass balance and ecological risks of antibiotics in subtropical shallow Lake Taihu, China[J]. Environmental Science: Processes & Impacts，2016，18（4）：500-513.
[169]YAN C, YANG Y, ZHOU J, et al. Antibiotics in the surface water of the Yangtze Estuary: Occurrence, distribution and risk assessment[J]. Environmental Pollution，2013，175：22-29.
[170]ZHOU L, YING G, ZHAO J, et al. Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China[J]. Environmental Pollution，2011，159（7）：1877-1885.
[171]ZHANG R, TANG J, LI J, et al. Occurrence and risks of antibiotics in the coastal aquatic environment of the Yellow Sea, North China[J]. Science of the Total Environment，2013，450-451：197-204.
[172]ZHOU H, LIU X, CHEN X, et al. Characteristics of removal of waste-water marking pharmaceuticals with typical hydrophytes in the urban rivers[J]. Science of the Total Environment，2018，636：1291-1302.
[173]ZHAO S, LIU X, CHENG D, et al. Temporal-spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China[J]. Science of the Total Environment，2016，569-570：1350-1358.
[174]剧泽佳，付雨，赵鑫宇，等. 喹诺酮类抗生素在城市典型水环境中的分配系数及其主要环境影响因子[J]. 环境科学，2022（2）：1-21.
[175]BOY R M, MAS P J, PETROVIC M, et al. Towards the understanding of antibiotic occurrence and transport in groundwater: Findings from the Baix Fluvià alluvial aquifer (NE Catalonia, Spain)[J]. Science of the Total Environment，2018，612：1387-1406.
[176]LI S, SHI W, LIU W, et al. A duodecennial national synthesis of antibiotics in China's major rivers and seas (2005-2016)[J]. Science of the Total Environment，2018，615：906-917.
[177]王祺. 磺胺抗生素在河流沉积物中的吸附/解吸特性研究[D]. 阜新：辽宁工程技术大学，2015：58.
[178]CHEN G, LIU X, TARTAKEVOSKY D, et al. Risk assessment of three fluoroquinolone antibiotics in the groundwater recharge system[J]. Ecotoxicology and Environmental Safety，2016，133：18-24.
[179]ZHANG Y, NIU Z, ZHANG Y, et al. Occurrence of intracellular and extracellular antibiotic resistance genes in coastal areas of Bohai Bay (China) and the factors affecting them[J]. Environmental Pollution，2018，236：126-136.
[180]QIAO Y, TAO J, CHEN C, et al. A miniature on-chip methane sensor based on an ultra-low loss waveguide and a micro-ring resonator filter[J]. Micromachines，2017，8（5）：160.
[181]NA G, ZHANG W, ZHOU S, et al. Sulfonamide antibiotics in the northern Yellow Sea are related to resistant bacteria: Implications for antibiotic resistance genes[J]. Marine Pollution Bulletin，2014，84（1-2）：70-75.
[182]LENG Y, XIAO H, LI Z, et al. Tetracyclines, sulfonamides and quinolones and their corresponding resistance genes in coastal areas of Beibu Gulf, China[J]. Science of the Total Environment，2020，714：136899.
[183]ERGIE A A, LENG Y, WANG J. Antibiotics and resistance genes in Awash River Basin, Ethiopia[J]. EcoHealth，2019，16（3）：441-453.
[184]颉亚玮，於驰晟，李菲菲，等. 某市污水厂抗生素和抗生素抗性基因的分布特征[J]. 环境科学，2021，42（01）：315-322.
[185]RODRIGUEZ M S, CHAMORRO S, MARTI E, et al. Occurrence of antibiotics and antibiotic resistance genes in hospital and urban wastewaters and their impact on the receiving river[J]. Water Research，2015，69：234-242.
[186]SONG W, LI J, FU C, et al. Establishment of sulfate radical advanced oxidation process based on Fe2+/O2/dithionite for organic contaminants degradation[J]. Chemical Engineering Journal，2021，410：128204.
[187]SONG W, LI J, FU C, et al. Kinetics and pathway of atrazine degradation by a novel method: Persulfate coupled with dithionite[J]. Chemical Engineering Journal，2019，373：803-813.
[188]LAI L, ZHOU P, ZHOU H, et al. Heterogeneous Fe(III)/Fe(II) circulation in FeVO4 by coupling with dithionite towards long-lasting peroxymonosulfate activation: Pivotal role of vanadium as electron shuttles[J]. Applied Catalysis B: Environmental，2021，297：120470.
[189]刘成. 二硫化钼基复合材料的合成及其光催化性能研究[D]. 西安：西北大学，2019：180.
[190]WANG J, WANG Z, CHENG Y, et al. Molybdenum disulfide (MoS2): A novel activator of peracetic acid for the degradation of sulfonamide antibiotics[J]. Water Research，2021，201：117291.
[191]HU L, FLANDERS P M, MILLER P L, et al. Oxidation of sulfamethoxazole and related antimicrobial agents by TiO2 photocatalysis[J]. Water Research，2007，41（12）：2612-2626.
[192]EMILIO C A, GETTAR R, LITTER M I. Mechanism of degradation of nitrilotriacetic acid by heterogeneous photocatalysis over TiO2 and platinized TiO2[J]. Journal of Applied Electrochemistry，2005，35（7-8）：733-740.
[193]CALZA P. Photocatalytic transformations of sulphonamides on titanium dioxide[J]. Applied Catalysis B: Environmental，2004，53（1）：63-69.
[194]LI J, ZHOU Z, LI X, et al. Synergistically boosting sulfamerazine degradation via activation of peroxydisulfate by photocatalysis of Bi2O3-TiO2/PAC under visible light irradiation[J]. Chemical Engineering Journal，2022，428：132613.
[195]PETALA A, ARVANITI O S, TRAVLOU G, et al. Solar light induced photocatalytic removal of sulfamethoxazole from water and wastewater using BiOCl photocatalyst[J]. Journal of Environmental Science and Health. Part a, Toxic/hazardous Substances & Environmental Engineering，2021，56（9）：963-972.
[196]CANONICA S, KOHN T, MAC M, et al. Photosensitizer method to determine rate constants for the reaction of carbonate radical with organic compounds[J]. Environmental Science & Technology，2005，39（23）：9182-9188.
[197]AL-RASHEED R, CARDIN D J. Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: Influence of TiO2, temperature, pH, and air-flow[J]. Chemosphere，2003，51（9）：925-933.
[198]LI D, ZHANG N, YUAN R, et al. Effect of wavelengths on photocatalytic oxidation mechanism of sulfadiazine and sulfamethoxazole in the presence of TiO2[J]. Journal of Environmental Chemical Engineering，2021，9（5）：106243.