Trace determination of sulfonamide antibiotics and their acetylated metabolites via SPE-LC-MS/MS in wastewater and insights from their occurrence in a municipal wastewater treatment plant.

Antibiotics have drawn much attention as their wide usage in humans and animals may result in microbial resistance, which is a huge threat to humans' health. Studies on the occurrence and removals of antibiotics in wastewater treatment plants have been widely performed, but very few covered their main acetylated metabolites. This study developed an effective analytical method for the trace determination of four sulfonamides and three acetylated metabolites in municipal wastewaters, which was validated by linearity (R2 > 0.995), sensitivity (limit of quantification, LOQ < 0.78 ng/L), recovery (77.7%-148.1%) and precision (relative standard deviation, RSD < 9.6%). All sulfonamides and their acetylated metabolites were detected in municipal wastewaters including influent, primary settling tank and effluent. Removal performances of sulfapyridine (SP), sulfadiazine (SDZ), sulfamethoxazole (SMZ), and N4-acetyl sulfadiazine (AC-SDZ) in the municipal wastewater treatment plant were moderate or excellent, whereas the corresponding removals of sulfamethazine (SM2), N4-acetyl sulfapyridine (AC-SP), and N4-acetyl sulfamethazine (AC-SM2) were poor. The calculated poor removal of SM2 might be attributed to its fluctuation in raw wastewater, whereas the poor removals of AC-SP and AC-SM2 may be due to re-transformation from their parent sulfonamides. Our results showed that monitoring of acetylated sulfonamides in municipal wastewater is important for two reasons. One is that acetylated metabolites are good biomarkers for wastewater-based epidemiology when they are combined with their corresponding parent sulfonamides. The other is that the potential risk of sulfonamides in effluent to the natural environment cannot be accurately evaluated unless their acetylated metabolites are also accounted. This report is the first to address the potential risk of acetylated sulfonamides in effluent of wastewater treatment plants.

Fast trace determination of nine odorant and estrogenic chloro- and bromo-phenolic compounds in real water samples through automated solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

A fast and reliable method was developed for simultaneous trace determination of nine odorous and estrogenic chloro- and bromo-phenolic compounds (CPs and BPs) in water samples using solid-phase extraction (SPE) coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS). For sample preparation, the extraction efficiencies of two widely applied cartridges Oasis HLB and Sep-Pak C18 were compared, and the Oasis HLB cartridge showed much better extraction performance; pH of water sample also plays important role on extraction, and pH = 2-3 was found to be most appropriate. For separation of the target compounds, small addition of ammonium hydroxide can obviously improve the detection sensitivity, and the optimized addition concentration was determined as 0.2%. The developed efficient method was validated and showed excellent linearity (R 2 > 0.995), low limit of detection (LOD, 1.9-6.2 ng/L), and good recovery efficiencies of 57-95% in surface and tap water with low relative standard deviation (RSD, 1.3-17.4%). The developed method was finally applied to one tap and one surface water samples and most of these nine targets were detected, but all of them were below their odor thresholds, and their estrogen equivalent (EEQ) were also very low.

Worldwide human daily intakes of bisphenol A (BPA) estimated from global urinary concentration data (2000-2016) and its risk analysis.

To evaluate BPA's potential risk to health, it is important to know human daily intake. This study describes a simple but effective method to estimate the levels of human BPA intake among four different populations based on urinary concentration data. Nationally, of the 30 countries examined, the top ten countries for adult intake were Italy, Sweden, Denmark, France, Cyprus, Australia, Israel, Ghana, Jamaica, and Belgium. When the urinary excretion sample size was large enough and over 1000, it was found that the national estimated BPA daily intakes in the child group among countries, showed a good linear relationship with those of their corresponding adult group. Except the infant group with limited data, the global estimated BPA daily intakes for children and pregnant women were 2 and 1.4 times that of the adult group. Although the national and global estimated BPA daily intakes were generally below the temporary tolerable daily intake (tTDI) recommended by the European Food Safety Authority (EFSA), but some normal individuals' daily intakes exceeded the tTDI.

Simultaneous determination of estrogenic odorant alkylphenols, chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry.

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R (2) > 0.989), low limit of detection (LOD, 0.002-0.5 µg/L), and excellent recoveries (76-126 %) with low relative standard deviation (RSD, 0.7-12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.

Levels of six antibiotics used in China estimated by means of wastewater-based epidemiology.

Due to lack of proper regulation, information about antibiotics consumption in many countries such as China is difficult to obtain. In this study, a simple method based on wastewater-based epidemiology was adopted to estimate their usage in four megacities of China. Six antibiotics (norfloxacin, ofloxacin, sulfamethoxazole, trimethoprim, erythromycin and roxithromycin), which are the most frequently consumed antibiotics in China, were selected as the targets. Based on our results, Chongqing had the largest total annual consumption of the selected six antibiotics among the four megacities, followed by Guangzhou, then Hong Kong, with Beijing having the least, with values of 4.4 g/y/P, 4.0 g/y/P, 1.6 g/y/P, and 1.3 g/y/P, respectively. Compared with the daily consumption per capita in Italy, the estimated consumption levels of the selected six antibiotics in four cities of China were 12-41 times those of Italy. Our results suggested that the consumption of antibiotics in China was excessive.

[A 32P application device for the treatment of condyloma acuminatum in the rectum].

OBJECTIVE: To investigate the use of a 32P application device (AD) in the treatment of condyloma acuminatum (CA) in the rectum, and to compare its clinical effect with that of the microwave therapy. METHODS: This study included 107 cases of CA in the rectum, 99 males and 8 females, aged 21-58 (33.6 +/- 9.4) years. Forty-six of the patients (the AD group) were treated with a self-made 32P application device, which, as a tube-shaped carrier of radionuclide 32P colloid, was fixed in the rectum at the diseased part for medication at 4.9-8.2 Gy for 3-5 hours once and 1-2 times a week. The other 61 (the microwave group) were treated by microwave burning under local anesthesia. Both groups of patients were followed up for over 3 months for comparison of the therapeutic results and observation of the stability and reliability of the 32P application device. RESULTS: The rates of cure, reoccurrence and adverse reaction were 84, 8%, 13.0% and 8.7% in the AD group, compared with 40.3%, 55.7% and 75.4% in the microwave group, with statistically significant differences between the two groups (P < 0.01). CONCLUSION: The 32P application device, with its advantages of low cost, easy operation, good effect, high safety and reliability, low recurrence, fewer adverse events and good acceptability, is highly valuable for the treatment of CA in the rectum.