Zhaoguang Yang

Mass loading and emission of thirty-seven pharmaceuticals in a typical municipal wastewater treatment plant in Hunan Province, Southern China

The occurrence, fate, mass loading and environmental emission of 37 pharmaceuticals were studied through an integrated approach involving both dissolved and adsorbed phase at a typical wastewater treatment plant in Hunan Province, Southern China. The results displayed the prevalence of 24 and 23 compounds in dissolved phase of influent and effluent, respectively. Fourteen compounds were found adsorbed onto sludge with a mean concentration ranging from 0.85 to 2900μg/kg dry weight. Twelve compounds exhibited high adsorption potential onto suspended particulate matter (SPM) with a mean fraction ranging from 8.8% (trimethoprim) to 97% (tetracycline). Furthermore, SPM showed a diverse absorbability in influent and effluent water circumstance. The overall elimination varied from -16% for lincomycin to 99% for paracetamol, while macrolides were able to withstand the whole treatment process. Mass balance analysis indicated that degradation was the predominant removal pathway for most compounds, and adsorption onto sludge combined with a minor portion of degradation explained for the reduction of tetracyclines and fluoroquinolones, whereas macrolides were recalcitrant to both two processes. The total mass loading was estimated to be up to 2800mg/d/1000 inhabitants and most compounds exhibited lower or comparable level comparing to the global published data. The total environmental emission was estimated up to be 1000mg/d/1000 inhabitants, and a value of 650mg/d/1000 inhabitants was obtained when considering merely the dissolved phase. This work would be helpful for the better understanding of ultimate fate and real pollution of pharmaceuticals in the water environment.

Distribution, contamination and accumulation of heavy metals in water, sediments, and freshwater shellfish from Liuyang River, Southern China

Heavy metal distributions in water, sediments, and freshwater shellfish collected from Liuyang River in China have been investigated. The concentrations of heavy metals including Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd, and Pb were determined by ICP-MS. The distribution pattern of heavy metals in sediments was different from that in water. Large coefficients of variation of heavy metal concentrations were observed in water due to the susceptibility to discharge fluctuation and seasonal variation. Multivariate statistical analysis such as Pearson’s correlation analysis, hierarchical cluster analysis (HCA), and principal component analysis (PCA) were employed to identify the possible sources of heavy metals in sediments. These heavy metals were categorized into three distinct groups, one was derived from natural existence and two were associated with anthropogenic activities. Five shellfish species including three species of gastropod mollusks (Parafossarulus eximius, Semisulcospira cancellata, and Pomacea canaliculata) and two species of bivalve mollusks (Corbicula fluminea and Anodonta woodiana) were collected and investigated. The distribution pattern of heavy metals in shellfish species was visualized by the nonmetric multidimensional scaling (NMDS) plot. The metal pollution index (MPI) values for the shellfish species were in the descending order of C. fluminea > A. woodiana > S. cancellata > P. eximius > P. canaliculata.

Analysis of metallic nanoparticles and their ionic counterparts in complex matrix by reversed-phase liquid chromatography coupled to ICP-MS

Developing quantification and characterization methodology for metallic nanoparticles (MNPs) and their ionic component in complex matrix are crucial for the evaluation of their environmental behavior and health risks to humans. In this study, reversed phase high performance liquid chromatography combined ICP-MS was established for the characterization of MNPs in complex matrix. The ionic component could be separated from NPs with the optimized parameters of aqueous mobile phase. Good linear relationship between average diameter and retention time of NPs was obtained using HPLC-ICP-MS and the size smaller than 40 nm could be determined with this method, the detected results were in accordance with TEM results. The low detection limit of AuNPs and Au(Ⅲ) (both in sub-μg/L level) showed that this method was promising for the characterization of AuNPs and Au(Ⅲ) in environmental water. The mass concentration of ionic Au(Ⅲ) in environmental water could be detected using the proposed HPLC-ICP-MS and the concentration of AuNPs was obtained by subtracting the Au(Ⅲ) concentration from the total Au (The concentration of total Au was detected by ICP-MS after microwave digestion). Furthermore this proposed HPLC-ICP-MS method and single particle-ICPMS (SP-ICP-MS) was used for the analysis of the Ag speciation in commercial antibacterial products.

Size characterization of silver nanoparticles after separation from silver ions in environmental water using magnetic reduced graphene oxide

This study involved the synthesis of magnetic reduced graphene oxide (M-rGO) using a co-precipitation method and examined its resultant adsorption properties for mixtures containing silver ions and silver nanoparticles (AgNPs). The results indicate that M-rGO preferentially adsorbs silver ions in mixtures containing AgNPs, enabling the size characterization of smaller AgNPs (<60nm) at ultra-trace concentration levels to be more attainable. The sorbents after adsorption could be easily recovered through an external magnet. The AgNPs retained in solution were characterized using single-particle ICPMS (SP-ICPMS). The adsorption behavior of silver ions on M-rGO was well fitted with the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, with the conclusion that the adsorption of silver ions occurred primarily through the chemical bond effect and the heterogeneous surface of the sorbent. Finally, the application of M-rGO with the approach developed herein to actual environmental water samples was successful.

Pharmaceutically active compounds in the Xiangjiang River, China: Distribution pattern, source apportionment, and risk assessment

The occurrence of 36 pharmaceutically active compounds in surface water of the Xiangjiang River was investigated in two seasons (n = 38). Twenty-five of these compounds were detected, with cefotaxime (maximum concentration 830 ng L-1) the most abundant compound followed by amoxicillin (maximum concentration 710 ng L-1). The spatiotemporal distribution was observed; indicating that pollution hotspots were mostly located in economically developed and densely populated regions such as Changsha City. Lower concentrations were found in summer than winter, which may be attributed to the dilution effect of a flood event and higher water temperatures. The distribution of pharmaceuticals was significantly correlated with temperature and ammonia nitrogen content. A principal component analysis-multiple linear regression model estimated that domestic sewage was the main source of pharmaceuticals, although the source composition varied among different sampling sites. Risk assessment was conducted using both individual and mixture models for preliminary identification of potential hazards. Sulfamethoxazole, clarithromycin, and azithromycin posed a high risk to algae, while sulfamethoxazole, trimethoprim, and erythromycin-H2O showed a medium risk to invertebrates. Moreover, the mixture risk quotients calculated using a concentration addition model ranged from 0.31 to 9.60 in winter, and from 0.06 to 0.61 in summer, indicating a potential risk to the aquatic environment. This study provides scientific support to policy-makers to establish contaminant management priorities and enriches the global data on emerging contaminants.

Species-specific bioaccumulation and correlated health risk of arsenic compounds in freshwater fish from a typical mine-impacted river

Arsenic (As) speciation and bioaccumulation in fish muscle tissues have been intensively investigated in marine ecosystem. However, little is known about these in freshwater fish. In this study, freshwater fish including 120 specimens and 8 species were collected from the Xiang River, a typical mine-impacted river in China. Six As species including arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenocholine (AsC) and arsenobetaine (AsB) were simultaneously separated and determined using HPLC-ICP-MS. The mean (±SD) concentration of total As (tAs) in the dried fish muscle was 0.748±0.651mg·kg-1. AsB was found as the predominant As species in most of the studied fish samples, in accordance with the reports in marine fish. However, the diversity of inorganic/organic As proportion observed in the studied freshwater fish species was larger than that in marine fish species due to greater spatial variability of As contamination, mobilization and origination in the studied catchments. The percentage of AsB (AsB%) in fish muscle was irrelevant to tAs concentration, while the percentage of iAs (iAs%) decreased with tAs concentration in a hyperbolic pattern. This can be attributed to restricted assimilation and accumulation of toxic iAs with increasing tAs concentration in fish. Chronic non-carcinogenic and carcinogenic health risks were evaluated through Monte-Carlo simulation. The result indicated that consuming freshwater fish in the Xiang River could cause considerable carcinogenic risk to local inhabitants.

Influence of filtration during sample pretreatment on the detection of antibiotics and non-steroidal anti-inflammatory drugs in natural surface waters

Owing to the ease and effectiveness of removing suspended substances (SSs), filtration has become a universal pretreatment step during water sample preparation. However, it can lead to the underestimation of contaminants if the targets easily associate with the SSs or filters. For the first time, this study comprehensively assessed issues related to filtration for the accurate quantification of 35 typical pharmaceuticals, including 28 antibiotics and seven non-steroidal anti-inflammatory drugs (NSAIDs), in water samples by comparing the effects of different filter materials, preservatives, and water matrices on the recoveries. The results showed that some sulfonamides and NSAIDs had an affinity for nylon filters, whereas trimethoprim and macrolides were easily retained on mixed cellulose ester filters. The use of glass fiber filter (0.7 μm) resulted in improved recovery of all the targets. Acidification promoted the adsorption of fluoroquinolones, tylosin, and roxithromycin on SSs, whereas 5% methanol resulted in desorption of macrolides from the SSs and other pharmaceuticals (sulfadiazine, trimethoprim, etc.) from the solid-phase extraction cartridges. Without additional detection of targets adsorbed on the SSs and filters, the addition of appropriate surrogates prior to filtration can help correct the loss.

Endocrine-disrupting compounds in the Xiangjiang River of China: Spatio-temporal distribution, source apportionment, and risk assessment

Endocrine-disrupting compounds (EDCs) were seasonally investigated in the surface water of the Xiangjiang River (south China) in order to understand their spatio-temporal distribution, source apportionment, and ecological risks. The occurrence of 21 EDCs were determined with liquid chromatography-tandem mass spectrometry in the water samples collected along the river over four seasons, and the results were statistically analyzed. The concentrations of progestagens, androgens, estrogens ranged from not detected (ND) to 98.3 ng L-1; while the concentrations of alkylphenols ranged from 0.8 to 3.1 × 103 ng L-1; and that of caffeine ranged from 0.1 to 49.8 ng L-1. The detection frequencies of bisphenol A, 4-tert-octylphenol, 4-n-nonylphenol, estrone, and 17β-estradiol were 95-100% during the four sampling campaigns. The seasonal and spatial variation trend of EDCs in the Xiangjiang River was noticeable. The concentration of EDCs in Yueyang section (downstream) was the highest in winter, while the concentration in Yongzhou (upstream) section was the lowest in spring. The concentration of EDCs in the Xiangjiang River was significantly correlated with the levels of the total organic carbon, water temperature, and dissolved oxygen. Source analysis indicated that untreated sewage was the major source of EDCs. Furthermore, the potential risks of EDCs in the surface water to aquatic organisms were assessed with the risk quotient method (European Commission, 2003), and the results indicated the highest ecological risk of 17β-estradiol in the Xiangjiang River.

Assessment of heavy metal contamination, distribution and source identification in the sediments from the Zijiang River, China

In this study, the contents of 10 heavy metals (Sb, Cd, Cr, Mn, Co, Ni, Cu, Zn, As, and Pb) in 49 sediment samples from the Zijiang River were determined by using inductively coupled plasma-optical emission spectrometry. Contamination indexes including geoaccumulation index, modified degree of contamination, sediment quality guidelines, potential ecological risk index, together with potential ecological risk factor were used to assess heavy metal contamination in the sediments of the Zijiang River. Pearsons correlation analysis and principal component analysis were used to identify the sources of heavy metals. The results indicated that the mean values of heavy metals in the Zijiang Rivers sediments were found to be significantly higher than the corresponding background values. But when comparing with that in other rivers in the world, they were at medium levels except for Sb. Furthermore, a comparison of the heavy metal concentrations and the consensus-based sediment quality guidelines showed that the heavy metal pollutions (Cd, Cr, Ni, Cu, Zn, As, and Pb) tended to occasionally pose harmful impacts on the ecosystem. The values of contamination indexes revealed that serious heavy metal contamination and relatively high potential ecological risks were mainly existed in the downstream of antimony mining and smelting factories (S23-S49). In addition, high potential ecological risks of Sb were observed in sampling sites that were close to those factories (S23, S24, S25, and S27), and high potential ecological risks of Cd were observed in the downstream (S37-S49). Basing on the Pearsons correlation analysis and principal component analysis, three main sources were identified. Co, Zn, Cd, and Cu contaminants were mainly derived from agricultural activities; As, Sb, Mn, and Pb mainly came from mining and smelting activities; Cr and Ni were mainly from natural sources.

Characterisation of silver release from nanoparticle-treated baby products

ABSTRACT We tested six kinds of commercially available baby products containing nano-silver and divided them into two categories: baby food containers and baby oral care products, according to usage. We measured the total mass of silver, particle size, particle number concentration and the mobility under different simulated conditions. The total mass of silver in baby products and migration solutions was quantified by ICP-MS analysis, and the size of the migrated particles was investigated by single particle ICP-MS and transmission electron microscopy-energy dispersive spectrometer. Nano-silver has different migration behaviour in different materials, and the total mass of silver released in 3% acetic acid was generally highest for plastic material, while highest in 10% ethanol for silicone material. For baby food containers and baby oral care products, the total amount of silver in the migration solutions varied from 2.98 to 126.46 ng/dm2 and from 2.01 to 2.83 ng/g, respectively. The research shows that the use of baby products containing silver may expose babies to silver nanoparticles. Graphical Abstract