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医院废水中常见的药物残留:膜生物反应器处理后通过质谱法对降解产物进行定量和定性分析

Popular pharmaceutical residues in hospital wastewater: quantification and qualification of degradation products by mass spectroscopy after treatment with membrane bioreactor.

作者信息

Chiarello M, Minetto L, Giustina S V Della, Beal L L, Moura S

机构信息

LBIOP-Laboratory of Biotechnology of Natural and Synthetics Products, Technology Department, Biotechnology Institute, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.

LATAM-Laboratory of Environmental Technology, Technology Department, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.

出版信息

Environ Sci Pollut Res Int. 2016 Aug;23(16):16079-89. doi: 10.1007/s11356-016-6766-2. Epub 2016 May 5.

Abstract

The occurrence of drugs in wastewater has been considered an imminent risk to the population, for the treatments used are usually ineffective. The presence of four popular drug residues (metformin, paracetamol, tetracycline, and enalapril) in hospital effluents, by using ultra-fast liquid chromatography tandem mass spectrometry (UFLC-MS/MS) with electrospray (ESI) ionization, and removal/degradation by membrane bioreactor (MBR) system are investigated in this study. For analysis method, all standard calibration curves showed satisfactory linearity (R (2) ≥ 0.993) within a relatively wide range. The recovery was between 70.4 and 105.0 %, and the relative standard deviation (RSD) values were within the ranges of 8.2 and 13.5 %. The effluent samples were collected at the end of the process treated in a bench-scale MBR treatment system and preconcentrated on solid-phase extraction (SPE) cartridges. Following that procedure, the chemical analysis demonstrated that the MBR system was effective in enalapril 94.3 ± 7.63 %, tetracycline 99.4 ± 0.02 %, and paracetamol 98.8 ± 0.86 % removal. However, the polar metformin was less effectively removed (35.4 ± 12.49 %). Moreover, the degradation products were investigated using high-resolution mass spectrometry (HRMS) by quadrupole-time of flight (Q-TOF), which has been indicated a tetracycline metabolite. In order to investigate the environmental impact, the wastewater potential risk was evaluated. The risk quotient (RQ) by measure environmental concentration (MEC) and its predicted no effect concentration (PNEC) ratio (RQ = MEC/PNEC) was between 0.003 (enalapril) to 0.815 (paracetamol). Finally, this work demonstrates that UFLC-MS/MS (ESI-Q) is a sensitive and selective method for drug analysis in wastewater and with ESI-Q-TOF has the accuracy required for determining the degradation products of these compounds. Also, it indicated that membrane bioreactor systems represent a new generation of processes that have proved to outperform conventional treatment showing better effluent quality. The removal capacity studied in this work demonstrates the efficiency of this process.

摘要

废水中药物的存在被认为对人群构成了紧迫风险,因为通常使用的处理方法往往无效。本研究通过采用超快速液相色谱串联质谱法(UFLC-MS/MS)和电喷雾(ESI)电离技术,对医院废水中四种常见药物残留(二甲双胍、对乙酰氨基酚、四环素和依那普利)的存在情况进行了调查,并研究了膜生物反应器(MBR)系统对这些药物的去除/降解效果。对于分析方法,所有标准校准曲线在相对较宽的范围内均显示出令人满意的线性关系(R (2) ≥ 0.993)。回收率在70.4%至105.0%之间,相对标准偏差(RSD)值在8.2%至13.5%范围内。在实验室规模的MBR处理系统处理过程结束时收集出水样品,并在固相萃取(SPE)柱上进行预浓缩。按照该程序,化学分析表明MBR系统对依那普利的去除率为94.3 ± 7.63%,对四环素的去除率为99.4 ± 0.02%,对对乙酰氨基酚的去除率为98.8 ± 0.86%。然而,极性较强的二甲双胍去除效果较差(35.4 ± 12.49%)。此外,使用四极杆飞行时间(Q-TOF)高分辨率质谱(HRMS)对降解产物进行了研究,结果表明存在一种四环素代谢物。为了调查环境影响,对废水的潜在风险进行了评估。通过测量环境浓度(MEC)及其预测无效应浓度(PNEC)的比值计算出的风险商(RQ)(RQ = MEC/PNEC)在0.003(依那普利)至0.815(对乙酰氨基酚)之间。最后,这项工作表明UFLC-MS/MS(ESI-Q)是一种用于废水中药物分析的灵敏且选择性的方法,而ESI-Q-TOF具有确定这些化合物降解产物所需的准确性。此外,研究表明膜生物反应器系统代表了新一代的处理工艺,已证明其性能优于传统处理工艺,出水水质更好。本研究中所研究的去除能力证明了该工艺的效率。

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