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Stormwater runoff typically contains significant quantities of metal contaminants that enter urban waterways over short durations and represent a potential risk to water quality. The origin of metals within the catchment and processes that occur over the storm can control the partitioning of metals between a range of different forms. Understanding the fraction of metals present in a form that is potentially bioavailable to aquatic organisms is useful for environmental risk assessment. To help provide this information, the forms and dynamics of metal contaminants in an urban system were assessed across a storm. Temporal patterns in the concentration of metals in dissolved and particulate (total suspended solids; TSS) forms were assessed from water samples, and diffusive gradients in thin-films (DGTs) were deployed to measure the DGT-labile time-integrated metal concentration. Results indicate that the concentrations of dissolved and TSS-associated metals increased during the storm, with the metals Al, Cd, Co, Cu, Pb and Zn representing the greatest concern relative to water quality guideline values (GVs). The portion of labile metal as measured by DGT devices indicated that during the storm a substantial fraction (∼98%) of metals were complexed and pose a lower risk of acute toxicity to aquatic organisms. Comparison of DGT results to GVs indicate that current GVs are likely quite conservative when assessing stormwater pollution risks with regards to metal contaminants. This study provides valuable insight into the forms and dynamics of metals in an urban system receiving stormwater inputs and assists with the development of improved approaches for the assessment of short-term, intermittent discharge events.

Dissolved organic matter (DOM) plays important roles in both abiotic and biotic processes within aquatic ecosystems, and these in turn depend on the quality of the DOM. We collected and characterized chromophoric DOM (CDOM) from different Australian freshwater types (circumneutral, naturally acidic and groundwater-fed waterways), climatic regions and seasons. CDOM quality was characterized using absorbance and fluorescence spectroscopy. Excitation emission scans followed by parallel factor (PARAFAC) analysis showed that CDOM was characterized by three main components: protein-like, fulvic-like and humic-like components commonly associated with various waters globally in the Openfluor database. Principal component analysis showed that CDOM quality varied between naturally acidic, circumneutral and groundwater-fed waters, with unique CDOM quality signatures shown for each freshwater type. CDOM quality also differed significantly within some sites between seasons. Clear differences in dominant CDOM components were shown between freshwater types. Naturally acidic waters were dominated by highly aromatic (as indicated by the specific absorbance co-efficient (SAC340) and the specific UV absorbance (SUVA254) values which ranged between 31 and 50 cm2 mg−1 and 3.9–5.7 mg C−1 m−1 respectively), humic-like CDOM of high molecular weight (as indicated by abs254/365 which ranged from 3.8 to 4.3). In contrast, circumneutral waters were dominated by fulvic-like CDOM of lower aromaticity (SAC340: 7–21 cm2 mg−1 and SUVA254: 1.5–3.0 mg C−1 m−1) and lower molecular weight (abs254/365 5.1–9.3). The groundwater-fed site had a higher abundance of protein-like CDOM, which was the least aromatic (SAC340: 2–5 cm2 mg−1 and SUVA254: 0.58–1.1 mg C−1 m−1). CDOM was generally less aromatic, of a lower molecular weight and more autochthonous in nature during the summer/autumn sampling compared to winter/spring. Significant relationships were shown between various CDOM quality parameters and pH. This is the first study to show that different freshwater types (circumneutral, naturally acidic and groundwater-fed) contain distinct CDOM quality signatures in Australia, a continent with unique flora and geology.

This study investigated the acute toxicity of nickel (Ni) to cardinal tetra (Paracheirodon axelrodi), within the three main water types of the Amazon basin: black (Rio Negro), white (Rio Solimoes) and clear (Rio Tapajos) during the wet and dry season at pH 7 (representative of white and clear rivers) and pH 4 (representative of black waters). The influence of dissolved organic carbon (DOC) quality on Ni toxicity within the three waters was also explored via the use of DOC isolates. Differences in water chemistry, DOC quality and ion concentrations were shown between waters and between seasons. Toxicity of Ni was shown to vary between river waters, seasons, and pHs. Ni was significantly less toxic during the dry season at pH 4 in all three river waters; for example, black water during the wet season had an LC50 of 9.72 mg Ni/L compared to 41.5 mg Ni/L during the dry season. At pH 7, contrasting effects in toxicity between seasons were shown between black and clear waters (black: wet = 28.9 mg/L, dry = 17.3 mg/L; clear: wet = 13.8 mg/L, dry = 24.1 mg/L). There were no significant differences in Ni toxicity for white waters at pH 7 (white: wet = 22.2 mg/L, dry = 21.8). Overall, Ni was shown to be more toxic at pH 7 than at pH 4 except in black water during the wet season. Toxicity of Ni at pH 4 was positively related to DOC concentration and amount of humic-like and fulvic-like DOC and negatively related to fluorescence index. Therefore, at pH 4, Ni is more toxic in waters containing more allochthonous DOC, consisting of higher amounts of humic-like and fulvic-like components. LC50 values for the different DOC concentrates at the same DOC concentration of 4.5 mg/L (black: 26.8 mg/L; white: 73.3 mg/L; clear: 49.2) support the river water findings at pH 4 (Ni more toxic in presence of black DOC) indicating that DOC quality alone can influence Ni toxicity at this pH.