Chronic sublethal exposure to silver nanoparticles disrupts thyroid hormone signaling during Xenopus laevis metamorphosis.

Nanoparticles (NPs) are engineered in the nanoscale (<100 nm) to have unique physico-chemical properties from their bulk counterparts. Nanosilver particles (AgNPs) are the most prevalent NPs in consumer products due to their strong antimicrobial action. While AgNP toxicity at high concentrations has been thoroughly investigated, the sublethal effects at or below regulatory guidelines are relatively unknown. Amphibian metamorphosis is mediated by thyroid hormone (TH), and initial studies with bullfrogs (Rana catesbeiana) indicate that low concentrations of AgNPs disrupt TH-dependent responses in premetamorphic tadpole tailfin tissue. The present study examined the effects of low, non-lethal, environmentally-relevant AgNP concentrations (0.018, 0.18 or 1.8 µg/L Ag; ∼10 nm particle size) on naturally metamorphosing Xenopus laevis tadpoles in two-28 day chronic exposures beginning with either pre- or prometamorphic developmental stages. Asymmetric flow field flow fractionation with online inductively coupled plasma mass spectrometry and nanoparticle tracking analysis indicated a mixture of single AgNPs with homo-agglomerates in the exposure water with a significant portion (∼30-40%) found as dissolved Ag. Tadpoles bioaccumulated AgNPs and displayed transient alterations in snout/vent and hindlimb length with AgNP exposure. Using MAGEX microarray and quantitative real time polymerase chain reaction transcript analyses, AgNP-induced disruption of five TH-responsive targets was observed. The increased mRNA abundance of two peroxidase genes by AgNP exposure suggests the presence of reactive oxygen species even at low, environmentally-relevant concentrations. Furthermore, differential responsiveness to AgNPs was observed at each developmental stage. Therefore, low concentrations of AgNPs had developmental stage-specific endocrine disrupting effects during TH-dependent metamorphosis.

Monitoring for contaminants of emerging concern in drinking water using POCIS passive samplers.

Contaminants of emerging concern (CEC) have been detected in drinking water world-wide. The source of most of these compounds is generally attributed to contamination from municipal wastewater. Traditional water sampling methods (grab or composite) often require the concentration of large amounts of water in order to detect trace levels of these contaminants. The Polar Organic Compounds Integrative Sampler (POCIS) is a passive sampling technology that has been developed to concentrate trace levels of CEC to provide time-weighted average concentrations for individual compounds in water. However, few studies to date have evaluated whether POCIS is suitable for monitoring contaminants in drinking water. In this study, the POCIS was evaluated as a monitoring tool for CEC in drinking water over a period of 2 and 4 weeks with comparisons to typical grab samples. Seven "indicator compounds" which included carbamazepine, trimethoprim, sulfamethoxazole, ibuprofen, gemfibrozil, estrone and sucralose, were monitored in five drinking water treatment plants (DWTPs) in Ontario. All indicator compounds were detected in raw water samples from the POCIS in comparison to six from grab samples. Similarly, four compounds were detected in grab samples of treated drinking water, whereas six were detected in the POCIS. Sucralose was the only compound that was detected consistently at all five plants. The POCIS technique provided integrative exposures of CECs in drinking water at lower detection limits, while episodic events were captured via traditional sampling methods. There was evidence that the accumulation of target compounds by POCIS is a dynamic process, with adsorption and desorption on the sorbent occurring in response to ambient levels of the target compounds in water. CECs in treated drinking water were present at low ng L(-1) concentrations, which are not considered to be a threat to human health.

Removal of selected pharmaceuticals, personal care products and artificial sweetener in an aerated sewage lagoon.

A sewage lagoon serving the small municipality of Lakefield in Ontario, Canada was monitored in the summer, fall and winter to determine removals of carbamazepine, trimethoprim, sulfamethoxazole, ibuprofen, gemfibrozil, triclosan, sucralose, HHCB and AHTN. Concentrations of these compounds in untreated and treated wastewater were estimated by deploying POCIS and SPMD passive samplers in the sewage lagoon. Passive samplers were also deployed at several points upstream and downstream of the point of discharge from the lagoon into the Otonabee River. LC-MS/MS and GC-MS were utilized to determine the concentrations of pharmaceuticals and personal care products (PPCPs) and sucralose, an artificial sweetener. Among PPCPs sampled by POCIS, the highest estimated concentration in untreated wastewater was ibuprofen sampled during the fall, at an estimated concentration of 60.3 ng/L. The estimated average concentration of sucralose was 13.6 ng/L in the untreated wastewaters. Triclosan, HHCB and AHTN in SPMDs were highest during fall season, at 30, 1677 and 109 ng/L, respectively. For all compounds except gemfibrozil, carbamazepine and sucralose, removals were highest in the summer (83.0 to 98.8%) relative to removals in the fall (48.4 to 91.4%) and winter (14.0 to 78.3%). Finally, the estimated concentrations of carbamazepine, sulfamethoxazole, triclosan and HHCB were compared with predicted values obtained through application of the WEST® modeling tool, with a new model based on the River Water Quality Model No. 1 and extended with dynamic mass balances describing the fate of chemicals of emerging concern subject to a variety of removal pathways. The model was able to adequately predict the fate of these four compounds in the lagoon in summer and winter, but the model overestimated removals of three of the four test compounds in the fall sampling period. This lagoon was as effective at removing PPCPs as many conventional WWTPs, but removals were better during the summer.

A novel approach for determining total titanium from titanium dioxide nanoparticles suspended in water and biosolids by digestion with ammonium persulfate.

Titanium dioxide (i.e. TiO(2)) in nano-form is a constituent of many nanomaterials that are used in sunscreens, cosmetics, industrial products and in biomedical applications. Quantification of TiO(2) nanoparticles in various matrixes is a topic of great interest for researchers studying the potential health and environmental impacts of nanoparticles. However, analysis of TiO(2) as Ti(4+) is difficult because current digestion techniques require use of strong acids that may be a health and safety risk in the laboratory. To overcome this problem, we developed a new method to digest TiO(2) nanoparticles using ammonium persulfate as a fusing reagent. The digestion technique requires short times to completion and optimally requires only 1 g of fusing reagent. The fusion method showed >95% recovery of Ti(4+) from 6 µg mL(-1) aqueous suspensions prepared from 10 µg mL(-1) suspension of different forms of TiO(2,) including anatase, rutile and mixed nanosized crystals, and amorphous particles. These recoveries were greater than open hot-plate digestion with a tri-acid solution and comparable to microwave digestion with a tri-acid solution. Cations and anions commonly found in natural waters showed no significant interferences when added to samples in amounts of 10 ng to 110 mg, which is a much broader range of these ions than expected in environmental samples. Using ICP-MS for analysis, the method detection limit (MDL) was determined to be 0.06 ng mL(-1), and the limit of quantification (LOQ) was 0.20 ng mL(-1). Analysis of samples of untreated and treated wastewater and biosolids collected from wastewater treatment plants yielded concentrations of TiO(2) of 1.8 and 1.6 ng mL(-1) for the wastewater samples, respectively, and 317.4 ng mg(-1) dry weights for the biosolids. The reactions between persulfate ions and TiO(2) were evaluated using stoichiometric methods and FTIR and XRD analysis. A formula for the fusing reaction is proposed that involves the formation of sulfate radicals.

The toxicity of titanium dioxide nanopowder to early life stages of the Japanese medaka (Oryzias latipes).

In this study, fertilized Japanese medaka (Oryzias latipes) embryos were exposed from fertilization to 5 d post-hatch using static non-renewal assays to aqueous suspensions of titanium dioxide nanoparticles (nTiO2) ranging in nominal concentrations between 0 and 14 µg mL⁻¹. The average size of the nTiO2 in the stock solution before addition to the test treatments was 87 nm (±14 nm). TiO2 materials accumulated in a concentration dependent manner on the chorionic filaments of developing medaka embryos with evidence of pericardial edema occurring during embryo development. However, no significant (p > 0.05) increases in mortality relative to control treatments were observed for the nTiO2 exposed embryos. A concentration dependent increase in cumulative percent hatch was observed at 11 d, indicating that exposure to increasing concentrations of nTiO2 resulted in the premature hatch of medaka embryos. Post-hatch, a significant proportion of sac fry from the nTiO2 exposure groups exhibited moribund swimming behavior and these individuals also experienced greater mortality at 15 d post-hatch. Combined, these results demonstrate that exposure to nTiO2 can impact the development of early life stages of fish.