小诺霉素发酵废水好氧生物处理试验研究

对具有强抑制性污染物的抗生素小诺霉素发酵废水，选择活性污泥、粉末活性炭（ＰＡＣＴ）、纯氧曝气等３种好氧生物处理法进行了比较试验。根据实验结果，小诺霉素发酵废水的生物降解呈抑制动力学，采用Ｍａｒｑｕａｒｔ方法对动力学模式进行参数估计。ＰＡＣＴ能够有效地降低降解过程中微生物受到的抑制作用，从而明显地改善了生物处理过程动力学。     

HPLC-三重四级杆质谱法测定医疗废水中抗生素残留

采用固相萃取/高效液相色谱-三重四级杆质谱法同时测定医疗废水中的20种超痕量抗生素残留,通过优化试验条件,使方法在100μg/L～100μg/L范围内线性良好,方法检出限为024ng/L～122ng/L。空白水样和实际水样3个质量浓度水平的加标回收率分别为80.2%～108%和75.8%～114%,6次测定结果的RSD分别为2.4%～8.4%和1.7%～8.1%。将该方法用于测定重庆市2家三甲医院医疗废水中的超痕量抗生素残留,结果有11种抗生素检出,其余均为未检出。     

Degradation and removal methods of antibiotics from aqueous matrices--a review

Over the past few years, antibiotics have been considered emerging pollutants due to their continuous input and persistence in the aquatic ecosystem even at low concentrations. They have been detected worldwide in environmental matrices, indicating their ineffective removal from water and wastewater using conventional treatment methods. To prevent this contamination, several processes to degrade/remove antibiotics have been studied. This review addresses the current state of knowledge concerning the input sources, occurrence and mainly the degradation and removal processes applied to a specific class of micropollutants, the antibiotics. In this paper, different remediation techniques were evaluated and compared, such as conventional techniques (biological processes, filtration, coagulation, flocculation and sedimentation), advanced oxidation processes (AOPs), adsorption, membrane processes and combined methods. In this study, it was found that ozonation, Fenton/photo-Fenton and semiconductor photocatalysis were the most tested methodologies. Combined processes seem to be the best solution for the treatment of effluents containing antibiotics, especially those using renewable energy and by-products materials.     

Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.     

Occurrence and source analysis of typical veterinary antibiotics in manure, soil, vegetables and groundwater from organic vegetable bases, northern China

The residue of antibiotics is becoming an intractable environmental problem in many organic vegetable bases. However, their residual levels and distribution are still obscure. This work systematically analyzed the occurrence and migration of typical veterinary antibiotics in organic vegetable bases, northern China. The results showed that there was no obvious geographical difference in antibiotic distribution between soil and manure. A simple migration model can be easy and quick to predict the accumulation of antibiotics in soil. Antibiotics were mainly taken up through water transport and passive absorption in vegetables. The distribution of antibiotics in a plant was in the sequence leaf > stem > root, and performed biological accumulation. The residues of antibiotics in all samples in winter were significantly higher than those in summer. Overall, this work can lay the foundation for understanding ecological risk of antibiotics and their potential adverse effects on human health by food chain.     

辽宁省生态清洁小流域抗生素监测及生态风险评估

于2021年10月对辽宁省生态清洁小流域抗生素的赋存浓度、分布特征进行了调查。采用风险商值法对小流域的抗生素生态风险进行评价。结果表明,辽宁省生态清洁小流域中8种抗生素均有不同程度检出,检出总质量浓度范围为0013～0.313 μg/L,平均值为0.072 μg/L;小流域中抗生素质量浓度均低于我国大部分河流和流域。不同类型抗生素空间分布规律差异明显,检测出的抗生素中,质量浓度最高的是罗红霉素（ROX）,检出率最高的是磺胺甲噁唑（SMX）;各监测点位抗生素组分的占比排序为：SMX＞ROX＞替米考星（TIC）＞氟苯尼考（FFC）;抗生素主要来源是畜禽养殖和生活污水。生态风险评价结果显示,ROX、脱水红霉素（ERY-H₂O）、诺氟沙星（NOR）和SMX存在高风险,其余种类呈现中、低风险。生态清洁小流域水体中暴露出的抗生素生态风险不容忽视,亟待进一步探究环境风险并采取有效的防治措施。     

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.     

Determination of antibiotics in sewage from hospitals, nursery and slaughter house, wastewater treatment plant and source water in Chongqing region of Three Gorge Reservoir in China

Sewage samples from 4 hospitals, 1 nursery, 1 slaughter house, 1 wastewater treatment plant and 5 source water samples of Chongqing region of Three Gorge Reservoir were analyzed for macrolide, lincosamide, trimethoprim, fluorouinolone, sulfonamide and tetracycline antibiotics by online solid-phase extraction and liquid chromatography-tandem mass spectrometry. Results showed that the concentration of ofloxacin (OFX) in hospital was the highest among all water environments ranged from 1.660 μg/L to 4.240 μg/L and norfloxacin (NOR, 0.136-1.620 μg/L), ciproflaxacin (CIP, ranged from 0.011 μg/L to 0.136 μg/L), trimethoprim (TMP, 0.061-0.174 μg/L) were commonly detected. Removal range of antibiotics in the wastewater treatment plant was 18-100% and the removal ratio of tylosin, oxytetracycline and tetracycline were 100%. Relatively higher removal efficiencies were observed for tylosin (TYL), oxytetracycline (OXY) and tetracycline (TET)(100%), while lower removal efficiencies were observed for Trimethoprim (TMP, 1%), Epi-iso-chlorotetracycline (EICIC, 18%) and Erythromycin-H₂O (ERY-H₂O, 24%). Antibiotics were removed more efficiently in primary treatment compared with those in secondary treatment.     

Biodegradation and bio-sorption of antibiotics and non-steroidal anti-inflammatory drugs using immobilized cell process

In the present study, the removal mechanisms of four antibiotics (sulfamethoxazole, sulfadimethoxine, sulfamethazine, and trimethoprim) and four non-steroidal anti-inflammatory drugs (acetaminophen, ibuprofen, ketoprofen, and naproxen) in immobilized cell process were investigated using batch reactors. This work principally explores the individual or collective roles of biodegradation and bio-sorption as removal routes of the target pharmaceuticals and the results were validated by various experimental and analytical tools. Biodegradation and bio-sorption were found as dominant mechanisms for the drug removal, while volatilization and hydrolysis were negligible for all target pharmaceuticals. The target pharmaceuticals responded to the two observed removal mechanisms in different ways, typically: (1) strong biodegradability and bio-sorption by acetaminophen, (2) strong biodegradability and weak bio-sorption by sulfamethoxazole, sulfadimethoxine, ibuprofen and naproxen, (3) low biodegradability and weak bio-sorption by sulfamethazine and ketoprofen, and (4) low biodegradability and medium bio-sorption by trimethoprim. In the sorption/desorption experiment, acetaminophen, sulfamethoxazole and sulfadimethoxine were characterized by strong sorption and weak desorption. A phenomenon of moderate sorption and well desorption was observed for sulfamethazine, trimethoprim and naproxen. Both ibuprofen and ketoprofen were weakly sorbed and strongly desorbed.     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).