Yiliang He

Emerging contaminants of public health significance as water quality indicator compounds in the urban water cycle.

The contamination of the urban water cycle (UWC) with a wide array of emerging organic compounds (EOCs) increases with urbanization and population density. To produce drinking water from the UWC requires close examination of their sources, occurrence, pathways, and health effects and the efficacy of wastewater treatment and natural attenuation processes that may occur in surface water bodies and groundwater. This paper researches in details the structure of the UWC and investigates the routes by which the water cycle is increasingly contaminated with compounds generated from various anthropogenic activities. Along with a thorough survey of chemicals representing compound classes such as hormones, antibiotics, surfactants, endocrine disruptors, human and veterinary pharmaceuticals, X-ray contrast media, pesticides and metabolites, disinfection-by-products, algal toxins and taste-and-odor compounds, this paper provides a comprehensive and holistic review of the occurrence, fate, transport and potential health impact of the emerging organic contaminants of the UWC. This study also illustrates the widespread distribution of the emerging organic contaminants in the different aortas of the ecosystem and focuses on future research needs.

Reactions of tetracycline antibiotics with chlorine dioxide and free chlorine

Tetracyclines (TCs) are a group of widely used antibiotics that have been frequently found in the aquatic environment. The potential reactions of TCs with common water disinfection oxidants such as chlorine dioxide (ClO(2)) and free available chlorine (FAC) have not been studied in depth and are the focus of this study. The oxidation kinetics of tetracycline, oxytetracycline, chlorotetracycline and iso-chlorotetracycline by ClO(2) and FAC are very rapid (with large apparent second-order rate constants k(app) = 2.24 × 10(5)-1.26 × 10(6) M(-1) s(-1) with ClO(2) and k(app) = 1.12 × 10(4)-1.78 × 10(6) M(-1) s(-1) with FAC at pH 7.0) and highly dependent on pH. Species-specific rate constants are obtained by kinetic modeling that incorporates pH-speciation of TCs and the oxidants (for FAC), and reveal that TCs primarily react with ClO(2) and FAC by their unprotonated dimethylamino group and deprotonated phenolic-diketone group. The modest difference in reactivity among the four TCs toward the oxidants is consistent with expectation and can be explained by structural influences on the two reactive moieties. Product evaluation shows that oxidation of TCs by ClO(2) leads to (hydr)oxylation and breakage of TC molecules, while oxidation of TCs by FAC leads to chlorinated and (hydr)oxylated products without any substantial ring breakage. Results of this study indicate that rapid transformation of TCs by oxidants such as ClO(2) and FAC under water and wastewater treatment conditions can be expected.

Effects of aqueous stable fullerene nanocrystals (nC60) on Daphnia magna: evaluation of sub-lethal reproductive responses and accumulation.

Concerns exist regarding the inadvertent release of engineered nanomaterials into natural systems, and the possible negative ecosystem response that may occur. Understanding sub-lethal effects may be particularly important to determining ecosystem responses as current levels of nanomaterial release are low compared to levels projected for the future. In this work, the sub-lethal effects and bioaccumulation of water stable, nanocrystalline fullerenes as C60, (termed nC60) were studied in Daphnia magna, a globally distributed, parthenogenetic zooplankton. Sub-lethal concentrations were first determined for both mature mother (LD50=0.4 mg L(-1)) and neonate (gestating) daphnids (0.2 mg L(-1)) in standard 48 h exposure tests. Subsequent experiments focused on the accumulation and effects (at temperatures of 18-28 degrees C) of nC60, during the D. magna reproductive cycle. The results demonstrate that upon sub-lethal exposure, the mortality rates of gestating daphnids increased with time and developmental stage. The maturation of daughter daphnids was negatively impacted. The mother daphnids were unable to reproduce again after exposure during pregnancy, and differential bioaccumulation occurred as a function of lipid content in the daphnia with the highest accumulation level of 7000 mg kg(-1) wet weight. Taken together, these results not only describe the accumulation and sub-lethal effects of nC60 on exposed daphnia, but also highlight the importance of sub-lethal exposure scenarios, which are critical to fully understanding the potential impact of fullerenes and other engineered nanoscale materials on natural systems.

Investigation of pharmaceuticals, personal care products and endocrine disrupting chemicals in a tropical urban catchment and the influence of environmental factors.

Previous studies showed the presence of multiple emerging organic contaminants (EOCs) in urban surface waters of Singapore even though there are no obvious direct wastewater discharges. In this study, we investigated the occurrence and distribution of 17 pharmaceuticals and personal care products (PPCPs) and endocrine disruptive compounds (EDCs) in a tropical urban catchment of Singapore. Monthly samples were collected from a reservoir and its 5 upstream tributaries during a 16-month period. Analysis of samples showed all sites had measurable PPCP and EDC concentrations, with caffeine (33.9-2980 ng/L), salicylic acid (5-838 ng/L), acetaminophen (<4-485.5 ng/L), BPA (<2-919.5 ng/L) and DEET (13-270 ng/L) being the most abundant. Marked differences in concentrations of target analytes between the reservoir and upstream tributaries were observed, and were tentatively attributed to the spatial differences in source inputs, water dilution capacity as well as natural attenuation of EOCs. Significant correlations between EOCs and conductivity, dissolved oxygen, chlorophyll a, turbidity, nutrients and cumulative precipitation were observed. These factors appeared to affect the distribution and attenuation of EOCs, depending on their physicochemical properties. Rainfall also influenced the temporal distribution of caffeine, BPA, triclosan, fipronil and DEET in the reservoir. Ecological risk assessment showed that caffeine, acetaminophen, estrone, BPA, triclosan and fipronil may warrant further survey. In particular, BPA levels exceeded the literature-based Predicted No-Effect Concentration (PNEC) value, highlighting the need for source control and/or water remediation in this urban catchment.

Effects of stable aqueous fullerene nanocrystal （nC60） on Daphnia magna： Evaluation of hop frequency and accumulations under different conditions

We investigated the effects of environmental factors and properties of water-stable crystal fullerene (nC60) on the uptake of nC60 by Daphnia magna based on known accumulation in our laboratory. This study was performed for seven days using different environmental factors including temperature, pH, water hardness, concentration (density of particle), and particle size. Results demonstrated that body burden of C60 increased with time in all experiments. Body burden of C60 increased with increasing concentration and particle size, and uptake of particles >100 nm reached their maximums more quickly than those <100 nm. Under high hardness in aqueous systems with lower pH and high temperature, uptake was higher than those under opposite conditions. Uptake in all batch tests reached balance within five days. Both nC60 properties and environmental factors influenced uptake of nC60 by D. magna in an aqueous system. Additionally, environmental factors may have affected accumulation by changing nC60 properties, which are critical to understand the accumulation of fullerenes in aqueous systems.

Effects of aqueous stable fullerene nanocrystal (nC60) on copper (trace necessary nutrient metal): Enhanced toxicity and accumulation of copper in Daphnia magna

Our focus herein is to evaluate the potential interaction between nC60 and copper, a trace necessary metal, in light of the impact on toxicity. The non-observable effects concentration (NOEC) of nC60 was confirmed as 100μgL(-1) before. When Daphnia magna was exposed to the mixture of copper solution and nC60 suspension (100μgL(-1)), LC50 of 48h was lower than that when they were exposed to copper solution alone. This result clearly showed the decrease in NOEC of copper at the presence of nC60. Cu(2+)-ATPase activity was enhanced at the presence of nC60, indicating that copper transport involved with the uptake, distribution and depuration in body was increased. We further conducted experiments on accumulation of copper in D. magna. The observed equilibrium copper concentration in D. magna in the mixture of 100μgL(-1) nC60 and 1μgL(-1) copper solution reached 131μg (kg wet weight)(-1), which was more than twice that in copper solution only: 60μg (kg wet weight)(-1). This result demonstrated that the accumulation of copper in D. magna was significantly enhanced at the presence of even low nC60 concentration. Experiments also showed that copper was quickly adsorbed onto nC60. The absorption of copper onto D. magna was statistically correlated to the absorption of nC60 onto D. magna; this might be caused by nC60 facilitating the transfer of copper into D. magna. The absorption and desorption of copper to nC60 (pH=5.0) reached equilibrium quickly, which may be involved with the co-bioaccumulation and decrease in NOEC of Cu(2+) and nC60.

A fullerene colloidal suspension stimulates the growth and denitrification ability of wastewater treatment sludge-derived bacteria

Fullerene (C60) is a nanoparticle that has been widely studied and applied in numerous commodities. However, there are concerns regarding its potential negative impact on the environment. A fullerene colloidal suspension (nC60) is known for its property of selectively inhibiting the growth of microorganisms. In this study, using denaturing gradient gel electrophoresis fingerprinting technology, we found that fullerene altered the structure of a sludge-derived microbial community. Specifically, the bacteria from Bacillus, Acidovorax and Cloacibacterium genera were enriched in abundance when supplemented with nC60 at pH 6.5 under aerobic conditions. The effects of the fullerene colloidal suspension on a strain of Bacillus isolated from the same microbial community were evaluated to further characterize the growth-stimulating effect of nC60. The biomass of cultures of this strain incubated with nC60 concentrations ranging from 3 mg L(-1) to 7 mg L(-1) was approximately twice that of the control during the stationary phase. The fullerene also induced higher superoxide dismutase activity in Bacillus cereus. Furthermore, the nitrate removal rate of B. cereus increased to nearly 55% in the presence of 5 mg L(-1) nC60, compared to 35% for the control. Meanwhile, the cumulative loading amount of nitrite was reduced from 33 μg mL(-1) to 25 μg mL(-1) by the addition of 5 mg L(-1) nC60. Our results demonstrate that the fullerene colloidal suspension is conditionally capable of promoting the growth and denitrification metabolism of certain bacteria, such as B. cereus. Fullerene might have both inhibitory and stimulatory effects on microorganisms in various environments.

Simultaneous analysis of multiple classes of antimicrobials in environmental water samples using SPE coupled with UHPLC-ESI-MS/MS and isotope dilution.

A robust and sensitive analytical method was developed for the simultaneous analysis of 21 target antimicrobials in different environmental water samples. Both single SPE and tandem SPE cartridge systems were investigated to simultaneously extract multiple classes of antimicrobials. Experimental results showed that good extraction efficiencies (84.5-105.6%) were observed for the vast majority of the target analytes when extraction was performed using the tandem SPE cartridge (SB+HR-X) system under an extraction pH of 3.0. HPLC-MS/MS parameters were optimized for simultaneous analysis of all the target analytes in a single injection. Quantification of target antimicrobials in water samples was accomplished using 15 isotopically labeled internal standards (ILISs), which allowed the efficient compensation of the losses of target analytes during sample preparation and correction of matrix effects during UHPLC-MS/MS as well as instrument fluctuations in MS/MS signal intensity. Method quantification limit (MQL) for most target analytes based on SPE was below 5ng/L for surface waters, 10ng/L for treated wastewater effluents, and 15ng/L for raw wastewater. The method was successfully applied to detect and quantify the occurrence of the target analytes in raw influent, treated effluent and surface water samples.

Biodegradation of nonylphenol polyethoxylates under sulfate-reducing conditions

Biodegradation behavior of nonylphenol polyethoxylates (NPEOs) under sulfate-reducing conditions was investigated. The results showed that NPEOs were readily degraded under sulfate-reducing conditions. These compounds were degraded via sequential removal of ethoxyl units to nonylphenol (NP) without forming carboxylated intermediates under sulfate-reducing conditions. The biodegradation of NPEOs under sulfate-reducing conditions was not inhibited even at very high initial concentrations of NPEOs. The maximum removal rate increased about 1.3 microM d(-1) for each 10 micromol increase in initial concentration. The decrease in temperature caused a sharp decrease in the removal efficiency of NPEOs. The temperature coefficient (Phi) for the biodegradation of NPEOs under sulfate-reducing conditions was 0.008. Severe accumulation of NP and short-chain NPEOs occurred when most NPEOs were removed and this accumulation led to an increase in the estrogenic activity. The highest estrogenic activity appeared on day 21 when the total concentration of these metabolites reached its top (18.03+/-4.73 microM). NP could inhibit the biodegradation of NPEOs under sulfate-reducing conditions only at relatively high concentration. These findings are of major environmental importance in terms of the environmental behavior of NPEO contaminants in natural environment.

Macrophage apoptosis induced by aqueous C60 aggregates changing the mitochondrial membrane potential

Fullerenes have been applied to various fields in recent years for their unique physicochemical properties. C60s potential environmental and health risks are therefore being investigated. This work presents the cytotoxicity of aqueous C60 aggregates (nC60) by using the mouse peritoneal macrophage (RAW264.7) as a model biological system. Cells incubated with nC60 showed a decrease in cell viability, and the quantities of cell apoptosis increased significantly in a dose-dependent and time-dependent manner. By TEM imaging cells were observed to be asymmetric and shrunken compared to control cells. nC60 was adsorbed onto the plasma membrane and apparent phagocytosis was observed after a 24h exposure. The intracellular reactive oxygen species (ROS) were quantified with the dichlorofluorescein diacetate (DCFH-DA) detection assay kit by flow cytometry and found to increase in treated cells. Membrane damage and lipid peroxidation were not observed, since both intracellular and extracellular MDA showed no variation. Detection of the mitochondrial membrane potential (MMP) by JC-1 assay kit showed that MMP had an obvious dose-dependent loss. We speculate that the nC60 aggregates induced apoptosis of macrophage by changing the mitochondrial membrane potential.