Wastewater and stormwater are both considered as critical pathways contributing microplastics (MPs) to the aquatic environment. However, there is little information in the literature about the potential influence of constructed wetlands (CWs), a commonly used wastewater and stormwater treatment system. This study was conducted to investigate the abundance and distribution of MPs in water and sediment at five CWs with different influent sources, namely stormwater and wastewater. The MP abundance in the water samples ranged between 0.4 ± 0.3 and 3.8 ± 2.3 MP/L at the inlet and from 0.1 ± 0.0 to 1.3 ± 1.0 MP/L at the outlet. In the sediment, abundance of MPs was generally higher at the inlet, ranging from 736 ± 335 to 3480 ± 4330 MP/kg dry sediment and decreased to between 19.0 ± 16.4 and 1060 ± 326 MP/kg dry sediment at the outlet. Although no significant differences were observed in sediment cores at different depth across the five CWs, more MPs were recorded in silt compared to sandy sediment which indicated sediment grain size could be an environmental factor contributing to the distribution of MPs. Polyethylene terephthalate (PET) fibres were the dominant polymer type found in the water samples while polyethylene (PE) and polypropylene (PP) fragments were predominantly recorded in the sediment. While the size of MPs in water varied across the studied CWs, between 51% and 64% of MPs in the sediment were smaller than 300 μm, which raises concerns about the bioavailability of MPs to a wider range of wetland biota and their potential ecotoxicological effects. This study shows that CWs can not only retain MPs in the treated water, but also become sinks accumulating MPs over time.

The inconsistency of available methods and the lack of harmonization in current microplastics (MPs) analysis in soils demand approaches for extraction and quantification which can be utilized across a wide variety of soil types. To enable robust and accurate assessment of extraction workflows, PET MPs with an inorganic tracer (Indium, 0.2% wt) were spiked into individual soil subgroups and standard soils with varying compositions. Due to the selectivity of the metal tracer, MPs recovery rates could be quickly and quantitatively assessed using ICP-MS. The evaluation of different methods specifically adapted to the soil properties were assessed by isolating MPs from complex soil matrices by systematically investigating specific subgroups (sand, silt, clay, non-lignified and lignified organic matter) before applying the workflow to standard soils. Removal of recalcitrant organic matter is one of the major hurdles in isolating MPs for further size and chemical characterization, requiring novel approaches to remove lignocellulosic structures. Therefore, a new biotechnological method (3-F-Ultra) was developed which mimics natural degradation processes occurring in aerobic (Fenton) and anaerobic fungi (CAZymes). Finally, a Nile Red staining protocol was developed to evaluate the suitability of the workflow for non-metal-doped MPs, which requires a filter with minimal background residues for further chemical identification, e.g. by μFTIR spectroscopy. Image analysis was performed using a Deep Learning tool, allowing for discrimination between the number of residues in bright-field and MPs counted in fluorescence mode to calculate a Filter Clearness Index (FCI). To validate the workflow, three well-characterized standard soils were analyzed applying the final method, with recoveries of 88% for MPs fragments and 74% for MPs fibers with an average FCI of 0.75. Collectively, this workflow improves our current understanding of how to adapt extraction protocols according to the target soil composition, allowing for improved MPs analysis in environmental sampling campaigns.

Plastic mulching and straw incorporation are common agricultural practices in China. Plastic mulching is suspected to be a significant source of microplastics in terrestrial environments. Straw incorporation has many effects on the storage of soil organic carbon (SOC) and greenhouse gas emissions, but these effects have not been studied in the presence of microplastic pollution. In this study, 365-day soil incubation experiments were conducted to assess the effects of maize straw and polyethylene microplastics on SOC fractions and carbon dioxide (CO₂) and nitrous oxide (N₂O) emissions in two different soils (fluvo-aquic and latosol). Against the background of straw incorporation, microplastics reduced the mineralization and decomposition of SOC, resulting in a microbially available SOC content decrease by 18.9%. In addition, microplastics were carbon-rich, but relatively stable and difficult to be used by microorganisms, thus increasing the mineral-associated SOC content by 52.5%. This indicated that microplastics had adverse effects on microbially available SOC and positive effects on mineral-associated SOC. Microplastics also decreased coarse particulate SOC (>250 μm), and increased non-aggregated silt and clay aggregated SOC (<53 μm). Furthermore, microplastics changed microbial community compositions, thereby reducing the CO₂ and N₂O emissions of straw incorporation by 26.5%–33.9% and 35.4%–39.7%, respectively. These results showed that microplastics partially offset the increase of CO₂ and N₂O emissions induced by straw incorporation. Additionally, the inhibitory effect of microplastics on CO₂ emissions in fluvo-aquic soil was lower than that in latosol soil, whereas the inhibitory effect on N₂O emissions had the opposite trend.

The performance of the radon (²²²Rn)-deficit technique has been evaluated at a site in which a complex DNAPL mixture (mostly hexachlorocyclohexanes and chlorobenzenes) has contaminated all four layers (from top to bottom: anthropic backfill, silt, gravel and marl) of the soil profile. Soil gas samples were collected at two depths (0.8 m and 1.7 m) in seven field campaigns and a total of 186 ²²²Rn measurements were performed with a pulse ionization detector. A statistical assessment of the influence of field parameters on the results revealed that sampling depth and atmospheric pressure did not significantly affect the measurements, while the location of the sampling point and ground-level atmospheric temperature did. In order to remove the bias introduced by varying field temperatures and hence to be able to jointly interpret ²²²Rn measurements from different campaigns, ²²²Rn concentrations were rescaled by dividing each individual datum by the mean ²²²Rn concentration of its corresponding field campaign. Rescaled ²²²Rn maps showed a high spatial correlation between ²²²Rn minima and maximum contaminant concentrations in the top two layers of the soil profile, successfully delineating the surface trace of DNAPL accumulation in the anthropic backfill and silt layers. However, no correlation could be established between ²²²Rn concentrations in superficial soil gas and contaminant concentration in the deeper two layers of the soil profile. These results indicate that the ²²²Rn-deficit technique is unable to describe the vertical variation of contamination processes with depth but can be an effective tool for the preliminary characterization of sites in which the distance between the inlet point of the sampling probe and the contaminant accumulation falls within the effective diffusion length of ²²²Rn in the affected soil profile.

Alprazolam, clonazepam and diazepam are drugs belonging to the benzodiazepine class. These drugs might be important environmental contaminants in aquatic media. A total understanding of behavior and fate of drugs in aquatic environment is not available for these and other drugs. Thus, in this work, a complete optimization of sample treatment and extraction of analytes from sediments and water was described, as well a study of sediment/water distribution comparing it with sample characteristics. Ultrasound for 10 min and 3 steps using 3 mL of extraction solvent were chosen as the stirring form for extraction. A methanol/water (1:1) solution pH 12 was the best extraction solvent. Aiming to eliminate interferences, an addition of 10 μL of NaCl 3.06 mol L⁻¹ was necessary after each step of extraction. Sediment and water samples were characterized, presenting different values on physical-chemical parameters. Six distinct sample sets of water and sediments were spiked with each benzodiazepine and analyzed. Kd values varied from 1.4 to 9.2 L kg⁻¹ for clonazepam, 1.8–11.5 L kg⁻¹ for alprazolam and 2.31–12 L kg⁻¹ for diazepam. A principal component analysis showed high dependence on Kd with sample characteristics mainly related to sediments. In the systems, whose sediments presented high levels of clay, silt and organic matter, the drugs presented a great interaction with the solid part of the system, increasing the Kd value. Koc values varied from 149.25 to 634.13 L kg⁻¹ for clonazepam, 186.57–852.48 L kg⁻¹ for alprazolam, and 194.68–1189.81 L kg⁻¹ for diazepam.

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca2+. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.

Sediment samples were collected to a depth of 60 cm along a 350-m sampling belt in a short-term-flooding riparian wetland in the Yellow River Delta of China in three sampling seasons. Contents of heavy metals were determined to investigate their spatial and temporal distributions, sources and ecotoxities. Our results showed that As contents in the top 20 cm sediments increased before decreasing along the sampling belt in summer, whereas they kept stable before increasing in fall and spring. Cd contents increased along the sampling belt in three sampling seasons, whereas Ni and Cr generally exhibited a decreasing tendency. Comparatively, Cu, Pb and Zn consistently increased at the first 50 m distance and then decreased before increasing from the distance of 150 m in summer and fall and increased to the maximum at the distance of 250 m and then showed a decrease in spring. Two “hotspots” of heavy metal accumulation in sediment cores along the belt were observed at the distance from 50 to 100 m in summer and at the distance from 200 to 300 m in spring. Most of sediment samples contained higher heavy metals in excess of threshold effect levels except for Zn and Pb in three sampling seasons and the values of toxic units in more than 30% of sediment samples exceeded 4 in summer. As, Ni and Cr had relatively higher contribution to the values of toxic units compared with other heavy metals in three sampling seasons. Multivariance analysis showed that As and Cd might originate from the same source and Cu, Zn, Cr, Pb and Ni might derive from another similar source. Cd was significantly correlated with salinity (p < 0.01) and pH (p < 0.05). Meanwhile, these heavy metals were also significantly correlated with other properties such as S, Al, TP, SOM and Silt + Clay.

The presence of Per-, Poly-fluoroalkyl substances (PFASs) in aquatic ecosystems has drawn broad concerns in the scientific community due to their biological toxicity. However, little has been explored regarding PFASs' removal in phytoplankton-dominated environments. This study aimed to create a simulated bacteria-algae symbiotic ecosystem to observe the potential transportation of PFASs. Mass distributions showed that sand (63–2000 μm), silt & clay (0–63 μm), the phycosphere (>3 μm plankton), and the free-living biosphere (0.22–3 μm plankton) contained 19.00, 7.78, 5.73 and 2.75% PFASs in their total mass, respectively. Significant correlations were observed between carbon chain lengths and removal rates (R² = 0.822, p < 10⁻⁴). Structural equation models revealed potential PFAS transportation pathways, such as water-phycosphere- free-living biosphere-sand-silt&clay, and water-sand-silt&clay (p < 0.05). The presence of PFASs decreased the bacterial density but increased algal density (p < 0.01) in the planktonic environment, and PFASs with longer carbon chain lengths showed a stronger enhancement in microbial community successions (p < 0.05). In algal metabolisms, chlorophyll-a and carotenoids were the key pigments that resisted reactive oxygen species caused by PFASs. PFBA (perfluorobutyric acid) (10.38–14.68%) and PFTeDA (perfluorotetradecanoic acid) (10.33–15.96%) affected bacterial metabolisms in phycosphere the most, while in the free-living biosphere was most effected by PFPeA (perfluorovaleric acid) (13.21–13.99%) and PFDoA (perfluorododecanoic acid) (10.04–10.50%). The results of this study provide new guidance measures for PFAS removal and management in aquatic environments.

The sedimentary history of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) over the past 140 years in a lake sediment core from Huixian karst wetland was reconstructed. The total PAHs and OCPs concentrations ranged from 40.0 to 210 ng g⁻¹ and 0.98 to 31.4 ng g⁻¹, respectively. The vertical distribution of PAHs and OCPs in different stages was great consistent with the history of regional socio-economic development and the usage of OCPs. As the indicators of socio-economic development, gross domestic product (GDP), population, energy consumption, highway mileage, and private vehicles correlated with the PAHs concentrations, indicating the impact of human activities on PAHs levels. The PAHs and OCPs concentrations were also affected by environmental changes in the wetland, as reconstructed by total organic carbon (TOC), sand, silt, clay, quartz, and calcite in sediments. Redundancy analysis (RDA) results showed TOC was the dominant factor to explain the concentrations of PAHs and OCPs with the explanation of 86.7% and 43.5%, respectively. In addition, TOC content had significantly positive correlation with PAHs (0.96, p < 0.01) and OCPs (0.78, p < 0.01). In particular, the significantly positive correlation (p < 0.05) between calcite and PAHs and OCPs inferred that karstification might play an important role in the migration of PAHs and OCPs in the karst area. Therefore, the lake in Huixian wetland tended to be a sink more than a source of PAHs and OCPs influenced by the increasing TOC content and karstification under climate warming.

Microplastics (MPs), as a new type of environmental pollutant, pose a serious threat to soil ecosystems. The activities of soil extracellular enzymes produced by microorganisms are the potential sensitive indicators of soil quality. However, little is known about the response mechanism of enzyme activities toward MPs on a long-term scale. Moreover, information on differences in enzyme activities across different soil aggregates is lacking. In this study, 150 days of incubation experiments and soil aggregate fractionation were combined to investigate the influence of MPs on extracellular enzyme activities in soil. 28% concentration of polyethylene with size 100 μm was adopted in the treatments added with MPs. The results show that MPs inhibited enzyme activities through changing soil nutritional substrates and physicochemical properties or through adsorption. Moreover, MPs competed with soil microorganisms for physicochemical niches to reduce microbial activity and eventually, extracellular enzyme activity. Enzyme activities in different aggregate-size fractions responded differently to the MPs exposure. The catalase in the coarse particulate fraction and phenol oxidase and β-glucosidase in the micro-aggregate fraction exerted the greatest response. With comparison, urease, manganese peroxidase, and laccase activities showed the greatest responses in the non-aggregated silt and clay fraction. These observations are believed to stem from differences in the key factors determining the enzyme activities in different aggregate-size fractions.The inhibitory pathway of microplastics on activities of extracellular enzymes in soil varies significantly across different aggregate fractions.