Jian-Liang Zhao

Comprehensive Evaluation of Antibiotics Emission and Fate in the River Basins of China: Source Analysis, Multimedia Modeling, and Linkage to Bacterial Resistance

Antibiotics are widely used in humans and animals, but there is a big concern about their negative impacts on ecosystem and human health after use. So far there is a lack of information on emission inventory and environmental fate of antibiotics in China. We studied national consumption, emissions, and multimedia fate of 36 frequently detected antibiotics in China by market survey, data analysis, and level III fugacity modeling tools. Based on our survey, the total usage for the 36 chemicals was 92700 tons in 2013, an estimated 54000 tons of the antibiotics was excreted by human and animals, and eventually 53800 tons of them entered into the receiving environment following various wastewater treatments. The fugacity model successfully predicted environmental concentrations (PECs) in all 58 river basins of China, which are comparable to the reported measured environmental concentrations (MECs) available in some basins. The bacterial resistance rates in the hospitals and aquatic environments were found to be related to the PECs and antibiotic usages, especially for those antibiotics used in the most recent period. This is the first comprehensive study which demonstrates an alarming usage and emission of various antibiotics in China.

Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China.

The occurrence of four classes of 17 commonly used antibiotics (including fluoroquinolones, tetracycline, sulfonamides, and macrolides) was investigated in the sediments of the Yellow River, Hai River and Liao River in northern China by using rapid resolution liquid chromatography-tandem mass spectrometry. Higher concentrations were detected for most antibiotics in the sediments of the Hai River than in the sediments of the other rivers. Norfloxacin, ofloxacin, ciprofloxacin and oxytetracycline in the three rivers were most frequently detected with concentrations up to 5770, 1290, 653 and 652 ng/g, respectively. High frequencies and concentrations of the detected antibiotics were often found in the downstream of large cities and areas influenced by feedlot and fish ponds. Good fitted linear regression equations between antibiotic concentration and sediment physicochemical properties (TOC, texture and pH) were also found, indicating that sediment properties are important factors influencing the distribution of antibiotics in the sediment of rivers.

Trace analysis of 28 steroids in surface water, wastewater and sludge samples by rapid resolution liquid chromatography–electrospray ionization tandem mass spectrometry

A sensitive rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS) method, combined with solid-phase extraction, ultrasonic extraction and silica gel cartridge cleanup, was developed for 28 steroids including 4 estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethynyl estradiol (EE2), diethylstilbestrol (DES)), 14 androgens (androsta-1,4-diene-3,17-dione (ADD), 17α-trenbolone, 17β-trenbolone, 4-androstene-3,17-dione, 19-nortestoserone, 17β-boldenone, 17α-boldenone, testosterone (T), epi-androsterone (EADR), methyltestosterone (MT), 4-hydroxy-androst-4-ene-17-dione (4-OHA), 5α-dihydrotestosterone (5α-DHT), androsterone (ADR), stanozolol (S)), 5 progestagens (progesterone (P), ethynyl testosterone (ET), 19-norethindrone, norgestrel, medroxyprogesterone (MP)), and 5 glucocorticoids (cortisol, cortisone, prednisone, prednisolone, dexamethasone) in surface water, wastewater and sludge samples. The recoveries of surface water, influents, effluents and sludge samples were 90.6-119.0% (except 5α-DHT was 143%), 44.0-200%, 60.7-123% and 62.6-138%, respectively. The method detection limits for the 28 analytes in surface water, influents, effluents and freeze-dried sludge samples were 0.01-0.24 ng/L, 0.02-1.44 ng/L, 0.01-0.49 ng/L and 0.08-2.06 ng/g, respectively. This method was applied in the determination of the residual steroidal hormones in two surface water of Danshui River, 12 wastewater and 8 sludge samples from two wastewater treatment plants (Meihu and Huiyang WWTPs) in Guangdong (China). Ten analytes were detected in surface water samples with concentrations ranging between 0.4 ng/L (17β-boldenone) and 55.3 ng/L (5α-DHT); twenty analytes in the wastewater samples with concentrations ranging between 0.3 ng/L (P) and 621 ng/L (5α-DHT); and 12 analytes in the sludge samples with concentrations ranging between 1.6 ng/g (E1) and 372 ng/g (EADR).

Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry.

An analytical method for phenolic endocrine disrupting chemicals and acidic pharmaceuticals in river water was developed using gas chromatography mass spectrometry (GC-MS) coupled with negative chemical ionization (NCI) technique, and used for the determination of these compounds in the Pearl Rivers (Liuxi, Zhujiang and Shijing Rivers). Derivatization using pentafluorobenzoyl chloride (PFBOCl) and pentafluorobenzyl bromide (PFBBr) before GC-MS analysis were applied and optimized for phenolic compounds and acidic compounds, respectively. The target compounds were analyzed for river waters from the upstream to downstream of the Pearl Rivers. Phenolic compounds 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), bisphenol-A (BPA), estrone (E1), estradiol (E2) and triclosan (TCS) were detected at trace or low levels in the water samples from Liuxi River and Zhujiang River. Diethylstilbestrol (DES) was not detected in the Pearl Rivers. The highest concentrations of the phenolic compounds were found in Shijing River, and they were 3150 ng/L for 4-t-OP, 11,300 ng/L for 4-NP, 1040 ng/L for BPA, 79 ng/L for E1, 7.7 ng/L for E2 and 355 ng/L for TCS, respectively. Only a few acidic pharmaceuticals were detected at low concentrations in water from Liuxi River and Zhujiang River, but the highest concentrations for the acidic pharmaceuticals were also found in Shijing River. The highest concentrations detected for clofibric acid, ibuprofen, gemfibrozil, naproxen, mefenamic acid and diclofenac were 17 ng/L, 685 ng/L, 19.8 ng/L, 125 ng/L, 24.6 ng/l and 150 ng/L, respectively. The results suggest Liuxi and Zhujiang Rivers are only slightly contaminated and can be used as drinking water sources, but Shijing River is heavily polluted by the wastewater from nearby towns.

Occurrence and fate of eleven classes of antibiotics in two typical wastewater treatment plants in South China

Wastewater treatment plants (WWTPs) are regarded as one of the most important sources of antibiotics in the environment. Two sampling campaigns over a period of one year in two wastewater treatment plants (plant A: activated sludge with chlorination, and plant B: oxidation ditch with UV) of Guangdong Province, China were carried out to assess the occurrence and fate of 11 classes of 50 antibiotics. The wastewater samples were extracted by Oasis HLB cartridges (6mL, 500 mg), while the solid samples (sludge and suspended solid matter) were extracted by ultrasonic-assisted extraction with solvents (acetonitrile and citric acid buffer), followed by an enrichment and clean-up step with solid-phase extraction using SAX-HLB cartridges in tandem. The results showed the presence of 20 and 17 target compounds in the influents and effluents, respectively, at the concentrations ranging from low ng/L to a few μg/L. Sulfamethoxazole, norfloxacin, ofloxacin, anhydro erythromycin and trimethoprim were most frequently detected in the WWTPs wastewaters. Twenty-one antibiotics were found in the sewage sludge from the two WWTPs at the concentrations up to 5800ng/g, with tetracycline, oxytetracycline, norfloxacin and ofloxacin being the predominant antibiotics. The total mass loads of antibiotics per capita in the two plants ranged from 494 to 901 μg/d/inhabitant (672±182 μg/d/inhabitant) in the influents, from 130 to 238 μg/d/inhabitant (175±45 μg/d/inhabitant) in the effluents and from 107 to 307 μg/d/inhabitant (191±87.9 μg/d/inhabitant) in the dewatered sludge, respectively. The aqueous removals for sulfonamides, macrolides, trimethoprim, lincomycin and chloramphenicol in the WWTPs were mainly attributed to the degradation processes, while those for tetracyclines and fluoroquinolones were mainly due to the adsorption onto sludge.

Simultaneous determination of four classes of antibiotics in sediments of the Pearl Rivers using RRLC-MS/MS

A simultaneous extraction and analysis method was developed for four classes of antibiotics: sulfonamides (SAs), macrolides (MLs), fluoroquinolones (FQs) and tetracyclines (TCs) in sediment. The antibiotics in the sediment were extracted by using an optimized mixed solution (citric buffer: acetonitrile, 50:50 v/v), and analyzed by rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS) equipped with electrospray ionization source in the positive mode. The recoveries for the antibiotics in the spiked sediment were: 66.3-123.5%, 48.2-72.0%, 61.8-160.4% and 60.6-151.9% for the SAs, TCs, FQs and MLs, respectively. The LOD ranged from 0.08 microg/kg to 4.2 microg/kg and LOQ from 0.26 microg/kg (erythromycin-H(2)O) to 14.01 microg/kg (norfloxacin). The developed analytical method was applied in the determination of the antibiotics in sediment samples collected from the Pearl Rivers, China. The antibiotics were found at the levels of microg/kg in the sediments of the three rivers. Ofloxacin was found to have the highest concentration of 1560 microg/kg in sediment. However, no significant seasonal variation could be found for the antibiotics in the sediments between wet season and dry season.

Occurrence and risks of triclosan and triclocarban in the Pearl River system, South China: from source to the receiving environment.

We investigated two commonly used antimicrobial agents triclosan (TCS) and triclocarban (TCC) in the Pearl River system in China (i.e., Liuxi, Zhujiang and Shijing Rivers) and four sewage effluents during dry and wet seasons. The median values for TCS and TCC were the highest in the surface water and sediments of the Shijing River, followed by the Zhujiang River and Liuxi River. Screening level risk assessment using the risk quotient (RQ) method showed that TCS and TCC in surface water posed median risks in the Zhujiang and Liuxi Rivers (RQs: 0.28-0.62 for TCS, and 0.15-0.80 for TCC) and high risks in the Shijing River (RQs: 5.15-9.55 for TCS, and 3.32-5.83 for TCC). Higher risks (RQs: 3.63-28.47 for TCS, and 3.13-24.54 for TCC) were found in the sediments than in surface water of the Pearl River system. The four sewage effluents and Shijing River as well as other urban streams in Guangzhou metropolitan area were identified as the sources of the two compounds in the main river Zhujiang River. The mass inventories of TCS and TCC in the Pearl River system indicate that the sediments are not only an important sink but also a potential source for the two compounds in surface water.

Distribution and accumulation of endocrine-disrupting chemicals and pharmaceuticals in wastewater irrigated soils in Hebei, China

This study investigated the occurrence of 43 emerging contaminants including 9 endocrine-disrupting chemicals and 34 pharmaceuticals in three sites in Hebei Province, north China. Each site has a wastewater irrigated plot and a separate groundwater irrigated plot for comparison purpose. The results showed that the concentrations of the target compounds in the wastewater irrigated soils were in most cases higher than those in the groundwater irrigated soils. Among the 43 target compounds, nine compounds bisphenol-A, triclocarban, triclosan, 4-nonylphenol, salicylic acid, oxytetracycline, tetracycline, trimethoprim and primidone were detected at least once in the soils. Preliminary environmental risk assessment showed that triclocarban might pose high risks to terrestrial organisms while the other detected compounds posed minimal risks. Irrigation with wastewater could lead to presence or accumulation of some emerging contaminants to some extent in irrigated soils.

Removal of selected endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) during ferrate(VI) treatment of secondary wastewater effluents

We investigated the removal efficiencies of 68 selected endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) spiked in a wastewater matrix by ferrate (Fe(VI)) and further evaluated the degradation of these micropollutants present in secondary effluents of two wastewater treatment plants (WWTPs) by applying Fe(VI) treatment technology. Fe(VI)treatment resulted in selective oxidation of electron-rich organic moieties of these target compounds, such as phenol, olefin, amine and aniline moieties. But Fe(VI) failed to react with triclocarban, 3 androgens, 7 acidic pharmaceuticals, 2 neutral pharmaceuticals and erythromycin-H(2)O.Thirty-one target EDCs and PPCPs were detected in the effluents of the two WWTPs with concentrations ranging from 0.2 ± 0.1 ng L(-1) to 1156 ± 182 ng L(-1).Fe(VI) treatment resulted in further elimination of the detected EDCs and PPCPs during Fe(VI) treatment of the secondary wastewater effluents. The results from this study clearly demonstrated the effectiveness of Fe(VI) treatment as a tertiary treatment technology for a broad spectrum of micropollutants in wastewater.

Assessing estrogenic activity in surface water and sediment of the Liao River system in northeast China using combined chemical and biological tools.

This paper investigated some selected estrogenic compounds (4-t-octylphenol: 4-t-OP; 4-nonylphenols: 4-NP; bisphenol-A: BPA; diethylstilbestrol: DES; estrone: E1; 17β-estradiol: E2; 17α-Ethinylestradiol: EE2; triclosan: TCS) and estrogenicity in the Liao River system using the combined chemical and in vitro yeast screen bioassay and assessed their ecological risks to aquatic organisms. The estrogenic compounds 4-t-OP, 4-NP, BPA, E1, E2 and TCS were detected in most of the samples, with their concentrations up to 52.1 2065.7, 755.6, 55.8, 7.4 and 81.3 ng/L in water, and up to 8.6, 558.4, 33.8, 7.9, <LOQ and 33.9 ng/g in sediment, respectively. However, DES and EE2 were not detected in the Liao River. The estrogen equivalents (EEQ) of the water and sediment samples were also measured by the bioassay. High estrogenic risks to aquatic organisms were found in the river sections of metropolitan areas and the lower reach of the river system.