The ionic strength of infiltration water changes with the seasonal alternation of irrigation sources. In this study, reactivity changes of birnessite-coated sand with the fluctuations of ionic strength of infiltration water (i.e. from groundwater to rainwater) and the involved mechanism were investigated through column experiments. Birnessite-coated sand was less reactive in groundwater than in rainwater because of the higher cation content and higher pH of groundwater. The cations in the groundwater were adsorbed on birnessite-coated sand and then desorbed in presence of a dilute aqueous solution represented by rainwater. The reactivity of the passivated birnessite-coated sand was recovered instantaneously, and approximately one-third of the pristine reactivity was restored. During recovery, Na⁺ desorption and lincomycin (LIN) removal both exhibited a two-stage reaction pattern. The LIN removal correlated with Na⁺ desorption (r = 0.99) so that the reactive sites that were binding 5.602 μmol of Na⁺ became available for 1 μmol of LIN removal. These results suggest that the reactivity of manganese oxides toward organic contaminant is associated with the ionic strength of infiltration water and indicate that the partial reactivity can be naturally restored.

Urban rivers play a vital role in global methane (CH₄) emissions. Previous studies have mainly focused on CH₄ concentrations in urban rivers with a large amount of organic sediment. However, to date, the CH₄ concentration in gravel-bed urban rivers with very little organic sediment has not been well documented. Here, we collected water samples from an oxic urban river (Xin'an River, China; annual mean dissolved oxygen concentration was 9.91 ± 1.99 mg L⁻¹) with a stony riverbed containing very little organic sediment. Dissolved CH₄ concentrations were measured using a membrane inlet mass spectrometer to investigate whether such rivers potentially act as an important source of atmospheric CH₄ and the corresponding potential drivers. The results showed that CH₄ was supersaturated at all sampling sites in the five sampling months. The mean CH₄ saturation ratio (ratio of river dissolved CH₄ concentration to the corresponding CH₄ concentration that is in equilibrium with the atmosphere) across all sampling sites in the five sampling months was 204 ± 257, suggesting that the Xin'an River had a large CH₄ emission potential. The CH₄ concentration was significantly higher in the downstream river than in the upstream river (p < 0.05), which suggested that human activities along the river greatly impacted the CH₄ level. Statistical analyses and incubation experiments indicated that algae can produce CH₄ under oxic conditions, which may contribute to the significantly higher CH₄ concentration in August 2020 (p < 0.001) when a severe algal bloom occurred. Furthermore, other factors, such as heavy rainfall events, dissolved organic carbon concentration, and water temperature, may also be vital factors affecting CH₄ concentration. Our study enhances the understanding of dissolved CH₄ dynamics in oxic urban rivers with very little organic sediment and further proposes feasible measures to control the CH₄ concentration in urban rivers.

Contribution of liquid water content (LWC) to the levels of the carcinogenic particulate nitro(so) compounds and the chemistry affecting LWC were investigated based on the observation of seven nitrosamines and two nitramines in rural (Seosan) and urban (Seoul) area in South Korea during October 2019 and a model simulation. The concentrations of both the total nitrosamines and nitramines were higher in Seosan (12.48 ± 16.12 ng/m³ and 0.65 ± 0.71 ng/m³, respectively) than Seoul (7.41 ± 13.59 ng/m³ and 0.24 ± 0.15 ng/m³, respectively). The estimated LWC using a thermodynamic model in Seosan (12.92 ± 9.77 μg/m³) was higher than that in Seoul (6.20 ± 5.35 μg/m³) mainly due to higher relative humidity (75 ± 9% (Seosan); 62 ± 10% (Seoul)) and higher concentrations of free ammonia (0.13 ± 0.09 μmol/m³ (Seosan); 0.08 ± 0.01 μmol/m³ (Seoul)) and total nitric acid (0.09 ± 0.07 μmol/m³ (Seosan); 0.04 ± 0.02 μmol/m³ (Seoul)) in Seosan while neither fog nor rain occurred during the sampling period. The relatively high concentrations of the particulate nitrosamines (>30 ng/m³) only observed probably due to the higher LWC (>10 μg/m³) in Seosan. It implies that aqueous phase reactions involving NO₂ and/or uptake from the gas phase enhanced by LWC could be promoted in Seosan. Strong correlation between the concentrations of nitrosodi-methylamine (NDMA), an example of nitrosamines, simulated by a kinetic box model including the aqueous phase reactions and the measured concentration of NDMA in Seosan (R = 0.77; 0.37 (Seoul)) indicates that the aqueous phase reactions dominantly enhanced the NDMA concentrations in Seosan. On the other hand, it is estimated that the formation of nitrosamines by aqueous phase reaction was not significant due to the relatively lower LWC in Seoul compared to that in Seosan. Furthermore, it is presumed that nitramines are mostly emitted from the primary emission sources. This study implies that the concentration of the particulate nitrosamines can be promoted by aqueous phase reaction enhanced by LWC.

The Wang Lake Wetland is a highly valued area that is protected due to its high biodiversity. The wetland has a complicated hydrological regime and is subject to frequent human disturbance. We hypothesize that fluctuating hydrology and human activities have varied contributions to the temporal and spatial variations of polycyclic aromatic hydrocarbons (PAHs) in the wetland. Soil (SS), sediment (SD), and water, to acquire dissolved phase (DP) and suspended particulate matter (SPM), samples were collected from eight locations during low- and high-flow periods to elucidate multimedia phase distribution and transport of PAHs. Following the onset of the rainy season, the concentration of SPM-associated PAHs increased significantly, while the DP PAHs remained stable. Individual PAH ratios showed that, although pyrogenic sources are common, petrogenic derived compounds are the main source of PAHs in the Wang Lake Wetland. During the high-flow period, the empirical values for logarithms of the organic carbon-normalized partition coefficients (log KOC) of individual PAH-congeners were lower than the corresponding field-observed log KOC values from the SPM-DP and SD-DP systems, reflecting the complexity in evaluating multi-phase PAH partitioning. During the high-flow period, temperature-driven changes may have changed the sediment from a sink to a source for some high molecular weight PAHs. It was determined that human activities governed the PAH loading in the low-flow period, whereas during high-flow conditions, increased rainfall, higher temperatures, and fishery activity are the main factors controlling PAH input to the Wang Lake Wetland.

This review summarizes the most relevant information on PBDEs’ occurrence and their impacts in cetaceans at global scale, with special attention on the species with the highest reported levels and therefore the most potentially impacted by the current and continuous release of these substances. This review also emphasizes the anthropogenic and environmental factors that could increase concentrations and associated risks for these species in the next future. High PBDE concentrations above the toxicity threshold and stationary trends have been related to continuous import of PBDE-containing products in cetaceans of Brazil and Australia, where PBDEs have never been produced. Non-decreasing levels documented in cetaceans from the Northwest Pacific Ocean might be linked to the increased e-waste import and ongoing production and use of deca-BDE that is still allowed in China. Moreover, high levels of PBDEs in some endangered species such as beluga whales (Delphinapterus leucas) in St. Lawrence Estuary and Southern Resident killer whales (Orcinus Orca) are influenced by the discharge of contaminated waters deriving from wastewater treatment plants. Climate change related processes such as enhanced long-range transport, re-emissions from secondary sources and shifts in migration habits could lead to greater exposure and accumulation of PBDEs in cetaceans, above all in those species living in the Arctic. In addition, increased rainfall could carry greater amount of contaminants to the marine environment, thereby, enhancing the exposure and accumulation especially for coastal species. Synergic effects of all these factors and ongoing emissions of PBDEs, expected to continue at least until 2050, could increase the degree of exposure and menace for cetacean populations. In this regard, it is necessary to improve current regulations on PBDEs and broader the knowledge about their toxicological effects, in order to assess health risks and support regulatory protection for cetacean species.

To better evaluate the potential risks of aquatic polycyclic aromatic compounds (PACs), multiple approaches have been implemented in this study to assess the human health and ecological risks of parent, nitrated and oxygenated polycyclic aromatic hydrocarbons (PAHs, NPAHs and OPAHs) in the surface water of Jialing and Yangtze Rivers in downtown Chongqing in southwestern China. The concentrations of ∑PAHs (334 ± 125 ng L⁻¹) were much higher than those of ∑OPAHs (20.2 ± 7.49 ng L⁻¹) in the two rivers, while NPAHs were barely detected. Concentrations of detected PACs were higher in wet season than dry season, probably resulted from the elevated particle input due to heavy rainfall in wet season. Concentrations of PAHs were higher in the particulate phase than dissolved phase, while OPAHs levels showed a reverse pattern. The partition coefficients (Kₚ) of PACs in the water-SPM (suspended particulate matter) system were mainly affected by SPM concentrations and octanol/water partition coefficients of specific PACs. Human health risks calculated from non-probabilistic risk assessment model and probabilistic risk assessment model based on Monte Carlo simulation showed similar data pattern with slight difference in absolute values. Both models revealed potential or even severe human health risks contributed mainly by dermal exposure to aquatic PACs in this study. Furthermore, these models also manifested that infant stage was highly sensitive for PAC exposure. Sensitivity analysis indicated that health risk results was most sensitive to Benzo[a]pyrene equivalent toxic concentration (BaPₑq), followed by showering time and daily water intake volume. Levels of ecological risks and contributions of individual PACs differed from models based on different quality values. The adequacy of toxicity data was crucial for the reliability of ecological risk assessment.