More than a decade ago, the Stockholm Convention on Persistent Organic Pollutants (POPs), one of the multilateral environmental agreements administered by the United Nations Environment Programme (UNEP), entered into force. The objective of this Convention is to protect human health and the environment by controlling the releases of POPs. According to its Article 16, the effectiveness of the Stockholm Convention shall be evaluated using comparable monitoring data on the presence of POPs as well as their regional and global environmental transport. Here, we present a time series analysis on atmospheric POP concentrations from 15 monitoring stations in North America and Europe that provide long-term data and have started operations between 1990 and 2003. We systematically searched for temporal trends and significant structural changes in temporal trends that might result from the provisions of the Stockholm Convention. We find that such structural changes do occur, but they are related mostly to effects of national regulations enforced prior to the implementation of the Stockholm Convention, rather than to the enforcement of the provisions laid out in the Convention. One example is that concentrations of polychlorinated biphenyls, many of which started to decrease rapidly during the 1990s. Also effects of chemical transport and fate, for instance the re-volatilization of POPs from secondary sources, are thought to be a cause of some of the observed structural changes. We conclude that a decade of air monitoring data has not been sufficient for detecting general and statistically significant effects of the Stockholm Convention. Based on these lessons, we present recommendations for the future operation of existing monitoring programs and advocate for a stricter enforcement of the provisions of the Stockholm Convention, in the current absence of proof for its effectiveness.

Waterborne metal uptake has been extensively studied and dietary metal assimilation is increasingly recognized in fish, whilst the interaction between the two uptake routes is largely overlooked. This study compared the waterborne Cu bioaccumulation (⁶⁵Cu as tracer) in a juvenile rabbitfish at different feeding regimes (starvation (SG), feeding normal diet (NDG) or diet supplemented with extra Cu (DCG)) to test the hypothesis that feeding can influence waterborne metal uptake in marine fish. NDG and DCG diet was fed as a single meal and then all fish were exposed to waterborne ⁶⁵Cu for 48 h, during which the time course sampling was conducted to determine ⁶⁵Cu bioaccumulation, chyme flow and dietary Cu assimilation. The results revealed that SG fish accumulated the highest ⁶⁵Cu, followed by NDG (61% of SG), whilst DCG fish accumulated the lowest ⁶⁵Cu (34% of SG). These results suggested a protective effect of feeding against waterborne Cu bioaccumulation. This effect was most notable between 10 min and 16 h when there was chyme in gastrointestinal tract (GT). Dietary Cu assimilation mainly occurred before 16 h after feeding. Waterborne ⁶⁵Cu influx rate in the GT was positively correlated with ⁶⁵Cu contents of chyme in NDG, whereas it was largely negatively correlated with ⁶⁵Cu contents of chyme in DCG. The waterborne Cu uptake in the GT was mainly influenced by the chyme flow and dietary Cu assimilation. Overall, our findings suggested that feeding has an important effect on waterborne metal uptake and that both the feeding status of the fish and the relative metal exposure through water and food should be considered in prediction of the metal bioaccumulation and biomonitoring programs.

Estuarine environment is complex and receives different contaminants from numerous sources that are persistent, bioaccumulative and toxic. The distribution, source, contamination and ecological risk status of heavy metals in sediment of Brisbane River, Australia were investigated. Sediment samples were analysed for major and minor elements using LA-ICP-MS. Principal component analysis and cluster analysis identified three main sources of metals in the samples: marine sand intrusion, mixed lithogenic and sand intrusion as well as transport related. To overcome inherent deficiencies in using a single index, a range of sediment quality indices, including contamination factor, enrichment factor, index of geo-accumulation, modified degree of contamination, pollution index and modified pollution index were utilised to ascertain the sediment quality. Generally, the sediment is deemed to be “slightly” to “heavily” polluted. A further comparison with the Australian Sediment Quality Guidelines indicated that Ag, Cr, Cu, Ni, Pb and Zn had the potential to rarely cause biological effects while Hg could frequently cause biological effects. Application of potential ecological risk index (RI) revealed that the sediment poses moderate to considerable ecological risk. However, RI could not account for the complex sediment behaviour because it uses a simple contamination factor. Consequently, a modified ecological risk index (MRI) employing enrichment factor is proposed. This provides a more reliable understanding of whole sediment behaviour and classified the ecological risk of the sediment as moderate to very high. The results demonstrate the need for further investigation into heavy metal speciation and bioavailability in the sediment to ascertain the degree of toxicity.

The internal loading of P is reported to be the main factor initiating algal blooms. However, there are only a few reports on the dynamic variation of labile P in the sediment and overlying water during the decomposition of algal. In addition, the widely perceived relationship between labile P and Fe was not supported by in situ obtained values in freshwater. Consequently, the in situ simultaneous measurement of diffusion gradients in thin-film techniques (DGT) was applied on a large scale to detect the mechanisms of labile P and Fe in a typical shallow lake (Lake Hongze). The newly developed ZrO-DGT and ZrO-Chelex DGT were combined to obtain the concentration of labile P and Fe. Results showed that decomposition of algal might be the main contributor for the concentration dots and peaks of labile P in sediment profiles, as well as for the high values on the horizontal heterogeneity index of labile P at the depth of 0–30 mm of the sediment. Moreover, there existed significant difference between the apparent diffusion fluxes of labile P and Fe across the sediment–water interface which obtained from June sampling and October sampling. The results of apparent diffusion flux in two periods indicated the sediments changed from “sink” to “source” for labile P, especially at Sites 4–8, 10, 13–14, and 18. However, the role of the labile Fe has no significantly variation in the values of the diffusion flux. This phenomenon also contributed to the poor relationship between labile P and Fe in the sediment which obtained from the October sampling. Accordingly, we conclude that algal decomposition might be essential for internal loading of P in this aquatic ecosystem, and that also be the reason for vicious circle of algal occurrence in the following year in the center of Lake Hongze.

The formaldehyde (FA) is a crosslinking agent that reacts with cellular macromolecules such as proteins, nucleic acids and molecules with low molecular weight such as amino acids, and it has been linked to inflammatory processes and oxidative stress. This study aimed to analyze the oxidative effects on pulmonary inflammatory response in Fischer rats exposed to different concentrations of FA. Twenty-eight Fischer rats were divided into 4 groups (N = 7). The control group (CG) was exposed to ambient air and three groups were exposed to different concentrations of FA: 1% (FA1%), 5% (FA5%) and 10% (FA10%). In the Bronchoalveolar Lavage Fluid (BALF), the exposure to a concentration of 10% promoted the increase of inflammatory cells compared to CG. There was also an increase of macrophages and lymphocytes in FA10% and lymphocytes in FA5% compared to CG. The activity of NADPH oxidase in the blood had been higher in FA5% and FA10% compared to CG. The activity of superoxide dismutase enzyme (SOD) had an increase in FA5% and the activity of the catalase enzyme (CAT) showed an increase in FA1% compared to CG. As for the glutathione system, there was an increase in total glutathione (tGSH), reduced glutathione (GSH) and oxidized glutathione (GSSG) in FA5% compared to CG. The reduced/oxidized glutathione ratio (GSH/GSSG) had a decrease in FA5% compared to CG. There was an increase in lipid peroxidation compared to all groups and the protein carbonyl formation in FA10% compared to CG. We also observed an increase in CCL2 and CCL5 chemokines in the treatment groups compared to CG and in serum there was an increase in CCL2, CCL3 and CCL5 compared to CG. Our results point out to the potential of formaldehyde in promoting airway injury by increasing the inflammatory process as well as by the redox imbalance.

Nitrogen deposition has been shown to have significant impacts on a range of vegetation types resulting in eutrophication and species compositional change. Data from a re-survey of 89 coastal sites in Scotland, UK, c. 34 years after the initial survey were examined to assess the degree of change in species composition that could be accounted for by nitrogen deposition. There was an overall increase in the Ellenberg Indicator Value for nitrogen (EIV-N) of 0.15 between the surveys, with a clear shift to species characteristic of more eutrophic situations. This was most evident for Acid grassland, Fixed dune, Heath, Slack and Tall grass mire communities and despite falls in EIV-N for Improved grass, Strand and Wet grassland. The increase in EIV-N was highly correlated to the cumulative deposition between the surveys, and for sites in south-east Scotland, eutrophication impacts appear severe. Unlike other studies, there appears to have been no decline in species richness associated with nitrogen deposition, though losses of species were observed on sites with the very highest levels of SOx deposition. It appears that dune vegetation (specifically Fixed dune) shows evidence of eutrophication above 4.1 kg N ha−1 yr−1, or 5.92 kg N ha−1 yr−1 if the lower 95% confidence interval is used. Coastal vegetation appears highly sensitive to nitrogen deposition, and it is suggested that major changes could have occurred prior to the first survey in 1976.

Phosphatization of ZnO nanoparticles (ZNPs) at various pHs and its influence on subsequent lead sorption were investigated. Results showed that, in presence of phosphate, both the chemical speciation and crystalline phase of ZNPs were pH dependent that most of them were converted to crystalline Zn3(PO4)2 at acidic pHs, but only little amorphous hopeites can be formed under alkaline condition. Phosphatization process significantly enhanced subsequent lead sorption with the order of acidic process > alkaline > pristine ZNPs. Spectroscopic analysis including ATR-FTIR and XPS revealed main mechanisms of lead phosphate precipitation and inner-sphere complexes for lead sorption on acidic and alkaline treatment products, respectively. The potential toxicity of ZNPs and heavy metals in eutrophic aquatic ecosystems would thus be reduced due to the ubiquitous phosphatization process. This study highlights the importance of environmental variables in exploring the environmental behavior and fate of heavy metals as well as nanoparticles in natural waters.

The occurrence and fate of 48 pharmaceuticals and personal care products (PPCPs) in three wastewater treatment plants (WWTPs) located in different urbanization areas in Xiamen, China was investigated over one year. Results showed that PPCPs were widely detected, but the major PPCPs in the influent, effluent, and sludge were different. Spatial and seasonal variations of PPCP levels in the influent and sludge were observed. The removal efficiencies for most PPCPs were similar among the three WWTPs, although they employed different biological treatment processes. Furthermore, the mass loadings per inhabitant of most pharmaceuticals had a positive correlation with the urbanization levels, indicating that most pharmaceutical usage was higher in the urban core compared to the suburban zones. The total mass loadings of all the 48 PPCPs in the effluent and waste sludge showed close proportions, which suggested the importance of proper waste sludge disposal to prevent a large quantity of PPCPs from entering the environment.

Aquatic sediments serve as an important sink for engineered nanomaterials (ENMs), such as metal oxide nanoparticles (MeO NPs) and carbon nanotubes (CNTs). Owing to their remarkable properties, ENMs demonstrate significant potential to disturb the adsorption behavior of other contaminants in aquatic sediments, thereby altering the bioavailability and toxicity of these contaminants. Thus far, most studies have investigated the effect of CNTs on the adsorption of other contaminants on sediments. Cerium dioxide nanoparticles (CeO2 NPs), as one of the important MeO NPs, are also inevitably discharged into aquatic sediments because of their widespread use. In this study, we investigated the adsorption behavior of Pb2+ on sediments spiked with CeO2 NPs at a weight ratio of 5.0%. The results showed that the adsorption rates at three stages occurring during adsorption clearly increase for sediments contaminated with CeO2 NPs. Moreover, the results obtained from the adsorption isotherms indicated that the Langmuir isotherm model best fits the isotherm data for both sediments and those contaminated with CeO2 NPs. After spiking the sediments with CeO2 NPs, the theoretical maximum monolayer adsorption capacity (Qmax) for Pb2+ increased from 4.433 to 4.995 mg/g and the Langmuir isotherm coefficient (KL) decreased from 8.813 to 7.730 L/g. The effects of CeO2 NPs on the surface charge and pore surface properties of sediments were also studied as these properties affect the adsorption of several chemicals in sediments. The results showed that pHzpc, SBET, Sext, and average pore size of sediments clearly decrease for sediments contaminated with CeO2 NPs. Hence, the strong adsorption capacity of CeO2 NPs and the changes of sediment surface charge and pore surface properties caused by CeO2 NPs are important factors affecting the adsorption behavior of Pb2+. The potential risk of Pb2+ in aquatic environment may increase with CeO2 NPs buried in sediments.

The presence of sulfonamide antibiotics in aquatic environments poses potential risks to human health and ecosystems. In the present study, a highly porous activated carbon was prepared by KOH activation of an anthracite coal (Anth-KOH), and its adsorption properties toward two sulfonamides (sulfamethoxazole and sulfapyridine) and three smaller-sized monoaromatics (phenol, 4-nitrophenol and 1,3-dinitrobenzene) were examined in both batch and fixed-bed adsorption experiments to probe the interplay between adsorbate molecular size and adsorbent pore structure. A commercial powder microporous activated carbon (PAC) and a commercial mesoporous carbon (CMK-3) possessing distinct pore properties were included as comparative adsorbents. Among the three adsorbents Anth-KOH exhibited the largest adsorption capacities for all test adsorbates (especially the two sulfonamides) in both batch mode and fixed-bed mode. After being normalized by the adsorbent surface area, the batch adsorption isotherms of sulfonamides on PAC and Anth-KOH were displaced upward relative to the isotherms on CMK-3, likely due to the micropore-filling effect facilitated by the microporosity of adsorbents. In the fixed-bed mode, the surface area-normalized adsorption capacities of Anth-KOH for sulfonamides were close to that of CMK-3, and higher than that of PAC. The irregular, closed micropores of PAC might impede the diffusion of the relatively large-sized sulfonamide molecules and in turn led to lowered fixed-bed adsorption capacities. The overall superior adsorption of sulfonamides on Anth-KOH can be attributed to its large specific surface area (2514 m²/g), high pore volume (1.23 cm³/g) and large micropore sizes (centered at 2.0 nm). These findings imply that KOH-activated anthracite coal is a promising adsorbent for the removal of sulfonamide antibiotics from aqueous solution.