Chemistry

This study focused on detecting 22 target anti-estrogenic and anti-androgenic compounds in surface waters influenced by both discharges of municipal wastewater and agricultural runoff in Canada and Argentina. Polar organic chemical integrative samplers (POCIS) were used to monitor the target compounds in surface waters. The removals of the target compounds in a municipal wastewater treatment plant (WWTP) in Canada were also evaluated. In both Canada and Argentina pesticides with potential anti-estrogenic and anti-androgenic activities were detected in the surface waters. The highest concentrations were found in Argentina (up to 1010 ng L-1) in areas impacted by heavy agricultural practices. Cyproterone acetate and bicalutamide were the only two anti-cancer drugs detected only at the Canadian study site, the Speed River, ON. In the Guelph WWTP, that discharges into the Speed River, these target compounds were not all efficiently removed (>70%) during treatment. Overall, this study provides insight to possible anti-estrogenic and anti-androgenic compounds that may be contributing to endocrine disrupting activities in surface waters.

Author Keywords: Anti-androgens, Anti-estrogens, Cancer Therapy Drugs, Current use pesticides, Pharmaceuticals and Personal Care Products, Polar Organic Chemical Integrative Samplers

Metal binding to dissolved organic matter (DOM) determines metal speciation and strongly influences potential toxicity. The understanding of this process, however, is challenged by DOM source variation, which is not always considered by most existing metal speciation models. Source determines the molecular structure of DOM, including metal binding functional groups. This study has experimentally showed that the allochthonous-dominant DOM (i.e. more aromatic and humic) consistently has higher level of Pb binding than the autochthonous-dominant DOM (i.e. more aliphatic and proteinaceous) by more than two orders of magnitude. This source-discrimination, however, is less noticeable for Zn and Cd, although variation still exceeds a factor of four for both metals. The results indicate that metal binding is source-dependent, but the dependency is metal-specific. Accordingly, metal speciation models, such as the Windermere Humic Aqueous Model (WHAM), needs to consider DOM source variations. The WHAM input of active fraction of DOM participating in metal binding (f) is sensitive to DOM source. The commonly-used f = 0.65 substantially overestimated the Pb and Zn binding to autochthonous-dominant DOM, indicating f needs to be adjusted specifically. The optimal f value (fopt) linearly correlates with optical indexes, showing a potential to estimate fopt using simple absorbance and/or fluorescence measurements. Other DOM properties not optically-characterized may be also important to determine fopt, such as thiol, which shows strong affinity to most toxic metals and whose concentrations are appreciably high in natural waters (< 0.1 to 400 nmol L-1). Other analytical techniques rather than Cathodic Stripping Voltammetry (CSV) are required to accurately quantify thiol concentration for DOM with concentration > 1 mg L-1. To better explain the DOM-source effects, the conditional affinity spectrum (CAS) was calculated using a Fully Optimized ContinUous Spectrum (FOCUS) method. This method not only provides satisfactory goodness-of-fit, but also unique CAS solution. The allochthonous-dominant DOM consistently shows higher Pb affinity than autochthonous-dominant DOM. This source-discrimination is not clearly observed for Zn and Cd. Neither the variability of affinity nor capacity can be fully explained by the variability of individual DOM properties, indicating multiple properties may involve simultaneously. Together, the results help improve WHAM prediction of metal speciation, and consequently, benefit geochemical modelling of metal speciation, such as Biotic Ligand Model for predicting metal toxicity.

Author Keywords: Dissolved organic matter, Metal binding, Source, Windermere Humic Aqueous Model

This study examines the influence of dissolved organic matter (DOM) on dissolved vanadium (V) speciation in the Churchill River and Great Slave Lake using diffusive gradients in thin film (DGT). Vanadium is commonly found in natural environments such as rivers, lakes and oceans. It regulates normal cell growth, but in excessive amounts, it can have toxic effects on human and aquatic organisms. The use of in situ, time integrated DGT devices allows to better (1) monitor the most bioavailable fraction of V, the DGT-labile V, in Arctic Rivers and (2) assess the influence of DOM on dissolved V speciation. Higher DGT-labile V was found in the the central regions of the Mackenzie River (MR), with an average of 7.7 ± 2.3 nM, likely due to sediment leaching and permafrost thawing. The Churchill River and Great Slave Lake (GSL) showed lower DGT-labile V levels (2.2 ± 1.6 nM and 3.6 ± 2.7 nM, respectively), compared to central regions in MR. The CR DGT-labile V concentrations was positively correlated to protein-like DOM concentration and abundance (r = 0.3, p < 0.05). The data collected from this study will help in developing new strategies regarding environmental health and impact assessments of environmentally hazardous waste that consist of potentially high levels of toxic vanadium species. Developments in the use of DGT devices as a sampling method will also aid in future studies involved in analyzing environmental health and specifically dissolved V species in natural waters.

Author Keywords: diffusive gradients in thin-films, dissolved organic matter, fluorescence, mass spectrometry, UV-Vis, vanadium