The Athabasca's oil sands exploitation is controversial due to its potential risks to water quality but little is known about the temporal changes in the most bioavailable fraction of metal, the free/labile species. In this study, diffusive gradient in thin films (DGT) and the Windermere Humic Aqueous Model (WHAM VII) equilibrium model were used to examine the temporal changes in free/labile metal (Cu, Ni, Zn, Pb) species in three tributaries of the north-flowing Athabasca River in the Athabasca oil sands region (AOSR). The influence of dissolved organic matter (DOM) composition (i.e. fulvic: humic ratio) on modeled Cu and Ni speciation showed a negligible effect on the labile concentration. The best agreements (92 ± 8%) between DGT-labile and WHAM calculated labile concentrations were found assuming the formation of iron oxyhydroxides (FeO(OH)). The agreement was only 70 ± 7% in the presence of inorganic colloidal aluminum oxyhydroxides (AlO(OH)) and in the absence of any inorganic colloids. Together these results suggest that a change in DOM composition had limited impacts on modeled free metal ion concentrations. Although the concentration of the main metal ligand (i.e. DOM), varied from 9 to 40 ppm, no significant temporal differences in the abundance of WHAM-modeled labile species were found, suggesting mobility and bioavailability of Cu, Ni, Pb and Zn were comparable over the 2003–2012 period.

Developed landscapes are exposed to changes in hydrology and water chemistry that limit their ability to mitigate detrimental impacts to coastal water bodies, particularly those that result from stormwater runoff. The elevated level of impervious cover increases not only runoff but also contaminant loading of nutrients, metals, and road salt used for deicing to water bodies. Here we investigate the impact that road salt has on denitrification in roadside environments. Sediments were collected from a series of forested and roadside wetlands and acclimated with a range of Cl− concentrations from 0 to 5000 mg L−1 for 96 h. Denitrification rates were measured by the isotope pairing technique using 15N–NO3−, while denitrifying community structures were compared using terminal restriction fragment length polymorphism (T-RFLP) of nitrous oxide reductase genes (nosZ). Chloride significantly (p < 0.05) inhibited denitrification in forested wetlands at a Cl− dosage of 2500 or 5000 mg L−1, but the decrease in denitrification rates was less and not significant for the roadside wetlands historically exposed to elevated concentrations of Cl−. The difference could not be attributed to other significant changes in conditions, such as DOC concentrations, N species concentrations, or pH levels. Denitrifying communities, as measured by T-RFs of the nosZ gene, in the roadside wetlands with elevated concentration of Cl− were distinctly different and more diverse compared to forested wetlands, and also different in roadside wetlands after 96 h exposures to Cl−. The shifts in denitrifying communities seem to minimize the decrease in denitrification rates in the wetlands previously exposed to Cl. As development results in more Cl− use and exposure to a broad range of natural or manmade wetland structures, an understanding of the seasonal effect of Cl on denitrification processes in these systems would aid in design or mitigation of the effects on N removal rates.

Transition metals in the fourth period of the periodic table of the elements are widely widespread in aquatic environments. They could often occur at certain concentrations to cause adverse effects on aquatic life and human health. Generally, parametric models are mostly used to construct species sensitivity distributions (SSDs), which result in comparison for water quality criteria (WQC) of elements in the same period or group of the periodic table might be inaccurate and the results could be biased. To address this inadequacy, the non-parametric kernel density estimation (NPKDE) with its optimal bandwidths and testing methods were developed for establishing SSDs. The NPKDE was better fit, more robustness and better predicted than conventional normal and logistic parametric density estimations for constructing SSDs and deriving acute HC5 and WQC for transition metals in the fourth period of the periodic table. The decreasing sequence of HC5 values for the transition metals in the fourth period was Ti > Mn > V > Ni > Zn > Cu > Fe > Co > Cr(VI), which were not proportional to atomic number in the periodic table, and for different metals the relatively sensitive species were also different. The results indicated that except for physical and chemical properties there are other factors affecting toxicity mechanisms of transition metals. The proposed method enriched the methodological foundation for WQC. Meanwhile, it also provided a relatively innovative, accurate approach for the WQC derivation and risk assessment of the same group and period metals in aquatic environments to support protection of aquatic organisms.

Many lakes and rivers are enriched with high levels of suspended sediments (SPS). Denitrification occurring on suspended sediments (DSS) may play an important role in nitrogen removal in water columns with high SPS concentrations. Poyang Lake, with dramatic hydrologic variations, has high spatial and seasonal variation of SPS, and we hypothesized that DSS and nitrogen removal in this lake would vary similarly. DSS in Poyang Lake was determined by the traditional acetylene-inhibition method combined with a batch mode assay. Laboratory simulation experiments were also conducted to examine the factors controlling denitrification occurring on SPS. Seasonally, DSS rates at 15 sampling sites in Poyang Lake were 0.63 ± 0.24, 0.29 ± 0.17, 0.25 ± 0.18, and 0.52 ± 0.37 μmol N·L−1·d−1, respectively in spring, summer, autumn, and winter. Spatially, average DSS rates were higher in the northern lake area, which is connected to the Yangtze River, than in the upstream and central lake area. Lowest DSS rates occurred in semi-closed bay and dish lakes. Spatial and seasonal variations of DSS rates were affected by a combination of factors, in which nitrate concentrations, SPS composition, and concentrations of organic-SPS were the most important. These influencing factors were seasonally dependent, with nitrate concentrations having stronger effects on DSS during wet seasons than dry seasons. Results from a multiple stepwise regression model also demonstrated that DSS tended to occur on fine particles (e.g., clay particles, <4 μm). Evaluation of annual nitrogen loss by DSS was estimated according to the seasonal water budget and DSS rates in Poyang Lake. The total nitrogen loss by DSS was estimated to be 10800 ± 6090 t, which accounted for 2.8–9.9% of the nitrogen input, and this proportion was comparable to nitrogen removal by sediment denitrification. This result confirms that DSS was an important nitrogen sink in this large, turbid lake.

Adsorption of aromatic compounds, including polycyclic aromatic hydrocarbons, nitrobenzenes, phenols, and anilines, on a bamboo biochar produced at 700 °C (Ba700) was investigated with the mechanism discussion by isotherm fitting using the Polanyi-theory based Dubinin–Ashtakhov (DA) model. Correlations of adsorption capacity (Q0) of organic compounds with their molecular sizes and melting points, as well as correlations of adsorption affinity (E) with their solvatochromic parameters (i.e., π* and αm), on the biochar, were developed and indicating that adsorption is captured by the pore filling mechanism and derived from the hydrophobic effects of organic compounds and the forming of π-π electron donor-acceptor (EDA) interactions and hydrogen bonding interactions of organic molecules with surface sites of the biochar. The effects of organic molecular sizes and melting points on adsorption capacity are ascribed to the molecular sieving effect and the packing efficiency of the organic molecules in the biochar pores, respectively. These correlations can be used to quantitatively estimate the adsorption of organic compounds on biochars from their commonly physicochemical properties including solvatochromic parameters, melting points and molecular cross-sectional area. The prediction using these correlations is important for assessing the unknown adsorption behaviors of new organic compounds and also helpful to guide the surface modification of biochars and make targeted selection in the environmental applications of biochars as adsorbents.

Neutral Polyfluoroalkyl substances (PFASs) in the atmosphere were measured during a cruise campaign over the northern South China Sea (SCS) from September to October 2013. Four groups of PFASs, i.e., fluorotelomer alcohols (FTOHs), fluorotelomer acrylates (FTAs), fluorooctane sulfonamides (FOSAs) and fluorooctane sulfonamidoethanols (FASEs), were detected in gas samples. FTOHs was the predominant PFAS group, accounting for 95.2–99.3% of total PFASs (ΣPFASs), while the other PFASs accounted for a small fraction of ΣPFASs. The concentrations of ΣPFASs ranged from 18.0 to 109.9 pg m−3 with an average of 54.5 pg m−3. The concentrations are comparable to those reported in other marine atmosphere. Higher concentrations of ΣPFASs were observed in the continental-influenced samples than those in other samples, pointing to the substantial contribution of anthropogenic sources. Long-range transport is suggested to be a major pathway for introducing gaseous PFASs into the atmosphere over the northern SCS. In order to further understand the fate of gaseous PFASs during transport, the atmospheric decay of neutral PFASs under the influence of reaction with OH radicals and atmospheric physical processes were estimated. Concentrations of 8:2 FTOH, 6:2 FTOH and MeFBSE from selected source region to the atmosphere over the SCS after long-range transport were predicted and compared with the observed concentrations. It suggests that the reaction with OH radicals may play an important role in the atmospheric decay of PFAS during long-range transport, especially for shorted-lived species. Moreover, the influence of atmospheric physical processes on the decay of PFAS should be further considered.

A series of numerical simulations are performed to study the pollutant and sediment transport in free surface channel flow. The present paper examines the dispersion of passive contaminants injected from a time periodic source in a fully developed turbulent flow. More precisely, the pulsation effects on the distribution behaviors of dissolved and particulate pollutants are analyzed and discussed. Simulations are carried out using a commercial Computational Fluid Dynamic (CFD) code, Fluent 6.3, which is based on the finite volume approach. The standard k−ε turbulence closure model is selected to simulate the turbulence generation and the Volume of Fluid (VOF) method is used to accurately capture the time varying free surface. The Discrete Phase Model (DPM) is used for capturing the movement of particles. Numerical results show that increasing pulsation amplitude and decreasing frequency generates higher dispersive effects in the concentration profiles of a dissolved pollutant. It is also concluded that, unlike dissolved substances, the particle transportation can be enhanced only for certain combinations of the pulsation amplitude and frequency due to the synchronization of the particle’s movement with the oscillating potential.•Increasing pulsation amplitude and decreasing frequency generates higher dispersive effects.•Particle transportation can be enhanced only for certain amplitude-frequency combinations.

To evaluate the influence of coal property and stove efficiency on the emissions of parent polycyclic aromatic hydrocarbons (pPAHs) and oxygenated PAHs (oPAHs) during the combustion, fifteen coal/stove combinations were tested in this study, including five coals of different geological maturities in briquette and chunk forms burned in two residential stoves. The emission factors (EFs) of pPAHs and oPAHs were in the range of 0.129–16.7 mg/kg and 0.059–0.882 mg/kg, respectively. The geological maturity of coal significantly affected the emissions of pPAHs and oPAHs with the lower maturity coals yielding the higher emissions. The chunk-to-briquette transformation of coal dramatically increased the emissions of pPAHs and oPAHs during the combustion of anthracite, whereas this transformation only elevated the emissions of high molecular weight PAHs for bituminous coals. The influence of stove type on the emissions of pPAHs and oPAHs was also geological-maturity-dependent. High efficiency stove significantly reduced the emissions of PAHs from those relatively high-maturity coals, but its influences on low-maturity coals were inconstant.